CN1946767A - Endless tubular polyimide film - Google Patents

Endless tubular polyimide film Download PDF

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Publication number
CN1946767A
CN1946767A CN200480042932.7A CN200480042932A CN1946767A CN 1946767 A CN1946767 A CN 1946767A CN 200480042932 A CN200480042932 A CN 200480042932A CN 1946767 A CN1946767 A CN 1946767A
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aromatic
tetracarboxylic acid
acid
semi
composition
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CN100545194C (en
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西浦直树
鞍冈隆志
丸市直之
吉田勉
金武润也
村上彻
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Gunze Ltd
Ube Corp
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Gunze Ltd
Ube Industries Ltd
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Abstract

A process for producing a high-quality nonconductive or semiconductive endless (jointless) tubular polyimide film simply and efficiently with high economy, etc. In particular, there is provided a nonconductive or semiconductive endless tubular polyimide film constituted of a polyimide produced from a component of aromatic diamine and a component of two or more aromatic tetracarboxylic acids composed of 15 to 55 mol% of asymmetric aromatic tetracarboxylic acid ingredient and 85 to 45 mol% of symmetric aromatic tetracarboxylic acid ingredient, wherein a given amount of carbon black is dispersed according to necessity, and there are further provided a process for producing the same, etc.

Description

Endless tubular polyimide film
Technical field
The endless tubular polyimide film and the manufacture method thereof of the non-conductive or semi-conductivity that the present invention relates to improve.The endless tubular polyimide film of semi-conductivity for example, is to wait as the intermediate duplication band that is used for the electrofax mode of color printer, color copy machine etc. to use.
Background technology
Dielectric tubular polyimide film generally is processed into band shape, for example, is well known that as the travelling belt of heating article or fixedly brings use as the electrofax mode.
The tubular polyimide film of semi-conductivity is that blending dispersion has conductive carbon black to form in non-conductive tubular polyimide film, for example, brings use as the intermediate duplication that duplicating machine, printer, facsimile recorder and printing press are used.
The method for making of the tubular polyimide film of and semi-conductivity non-conductive as these, known method is the film that the shaped material of regulation temporarily is configured as flat condition, the two ends of junctional membrane and be processed as the piped method then, and by the centrifugal injection molding once-forming method that is the endless tubular film.In addition, for example the application's applicant opens the spy and has also put down in writing the method for substantially not having this centrifugal injection molding of enforcement under the centrifugal force and forming in the 2000-263568 communique.
As the shaping raw material of these tubular polyimide films, in general, use is as polyamic acid (or the polyamic acid) solution of the high molecular (number-average molecular weight is generally about 10000～30000) of the polymer precursor of polyimide.
Above-mentioned polyamic acid solution specifically, for example is to make 1,2,4,5-benzene tertacarbonic acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,6, the aromatic tetracarboxylic acid's dianhydride and the p-penylene diamines, 4 of bonding anhydride group on point symmetry position of 7-naphthalene tetracarboxylic acid dianhydride etc., 4 '-diaminodiphenyl oxide, 4, the aromatic diamine of 4 '-diaminodiphenylmethane etc. is with equimolar amount, in organic polar solvent, under the low temperature that degree of imidisation does not take place, carry out polycondensation and make.
The method for making of polyimide film adopts 3 procedures usually: produce the polyamic acid solution as shaping raw material earlier, again this polyamic acid solution is configured as polyamide acid film, carry out imidization at last and obtain polyimide film.
But, owing in the above-mentioned polyamic acid solution that above-mentioned manufacturing process obtained, have working life (pot life), so just there is in preservation easy generating unit gradually divide gelation such shortcoming.High more easy more the carrying out of this gelation, temperature even also carry out along with the time at low temperatures, even the gelation denier also can be given as the physical property of the polyimide film of final product and bring baneful influence, also can cause the deterioration of planarity certainly.Particularly in being mixed with this film of conductive carbon black, make the changes in resistance increase.
In addition, the solvability of polyamic acid resin in organic polar solvent is limited, and existence can not the such shortcoming of high densityization (reaching 25 weight % at least as the non-volatile content concentration in the solution).
In addition, if add carbon black in polyamic acid solution, then viscosity will raise greatly, in dispersion machines such as ball mill, carry out sometimes by ball between the sooty that carries out of surging force disperse the difficulty that also can become.Usually, for carbon black is dispersed in the polyamic acid solution, pulverize by the sooty that dispersion machine carried out, must be with the carbon black of having taken apart because of the such surface phenomenon of the caused what is called of solvent " moistening ".Therefore, just take to come homodisperse sooty method by the heavy addition organic polar solvent.But, consequently, be the solution of the following lower concentration of 16 weight % with regard to containing high density sooty parent glue material solution, can only obtaining non-volatile content concentration.
And there is following shortcoming in the lower concentration polyamic acid solution: be difficult to the thicker film of once-forming, when needs were than multi-solvent, the evaporation of solvent is removed needed the more time.
In addition, as mentioned above, owing to need 3 procedures, so from the viewpoint of efficiency and economy, full operation required time and cost also have room for improvement.
Yet, open the manufacturing process of having put down in writing the use polyimide precursor composition in the flat 10-182820 communique the spy, this polyimide precursor composition is roughly to wait mixed monomer of mole with aromatic tetracarboxylic acid's composition and aromatic diamine composition, and this aromatic tetracarboxylic acid's composition be with asymmetry aromatic tetracarboxylic acid or its ester be main component (specifically, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid or its ester are 60 moles more than the %).And, this spy open disclose in the flat 10-182820 communique with this polyimide precursor composition coating curtain coating on the sheet glass, heat the method that (heating up) forms polyimide film interimly between 80～350 ℃, can mix silver powder, copper powder, carbon black etc. and use as conductive paste.
But, with the semiconductive polyimide film that above-mentioned manufacturing process was obtained, under the situation of intermediate duplication band that is used for employed electrofax modes such as the high-precision color printer of requirement, color copy machine etc., characteristics such as resistance have further room for improvement in recent years.
Summary of the invention
In view of above-mentioned prior art problems point, the object of the present invention is to provide a kind of tubular polyimide film of endless (do not have and connect seam) of high-quality non-conductive or semi-conductivity, and provide a kind of easy, efficient and make the method for this film economically.
The present inventor furthers investigate in order to solve above-mentioned problem, found that: by asymmetry aromatic tetracarboxylic acid or the symmetry aromatic tetracarboxylic acid of its ester and specified quantitative or aromatic tetracarboxylic acid's composition that its ester constituted of specified quantitative, the mixing solutions that is essentially free state that mixes with equimolar amount roughly with the aromatic diamine composition, this mixing solutions is configured as pipe with the spinning-shaping method, carry out heat treated and imidization can produce high-quality endless tubular polyimide film thus.
That is, the invention provides following non-conductive or semi-conductivity endless tubular polyimide film.
(1) a kind of endless tubular polyimide film is characterized in that,
Constitute by polyimide, this polyimide is that the aromatic tetracarboxylic acid's composition more than 2 kinds that the mixture by 85～45 moles of % of 15～55 moles of % of asymmetry aromatic tetracarboxylic acid composition and symmetry aromatic tetracarboxylic acid composition constitutes becomes branch to form with aromatic diamine
Its yield strength (σ Y) be more than the 120MPa, the ratio (σ of breaking tenacity and yield strength Cr/ σ Y) be more than 1.10.
(2) a kind of semi-conductivity endless tubular polyimide film, it is characterized in that, disperse black carbon forms in aromatic tetracarboxylic acid's composition more than 2 kinds that the mixture by 15～55 moles of % of asymmetry aromatic tetracarboxylic acid composition and 85～45 moles of % of symmetry aromatic tetracarboxylic acid composition constitutes and the formed polyimide of aromatic diamine composition, and its surface resistivity is 10 3～10 15Ω/.
(3) as (2) described semi-conductivity endless tubular polyimide film, it is characterized in that, the standard deviation of the logarithm conversion value of surface resistivity is in 0.2, the standard deviation of the logarithm conversion value of volume specific resistance is in 0.2, and the difference of the logarithm conversion value of surface resistivity and the logarithm conversion value of back side resistivity is in 0.4.
The present invention has above-mentioned feature, more particularly, comprises following first invention～the four invention.
A. first invention
The present inventor finds, by the symmetry aromatic tetracarboxylic acid of the asymmetry aromatic tetracarboxylic acid of specified quantitative or its ester and specified quantitative or aromatic tetracarboxylic acid's composition that its ester constituted, with the aromatic diamine composition with the mixing solutions that is essentially free state that roughly equimolar amount mixes in, the carbon black that disperses specified quantitative, with formed semiconductive polyimide precursor composition, be configured as pipe with the spinning-shaping method, carry out heat treated and imidization can be made high-quality semi-conductivity endless tubular polyimide film thus.
The present inventor finds based on this, by further research repeatedly, thereby finishes the present invention (below be also referred to as " first invention ").
That is, first invention provides following non-conductive or semi-conductivity endless tubular polyimide film and manufacture method thereof.
(4) a kind of manufacture method of endless tubular polyimide film, it is characterized in that, aromatic tetracarboxylic acid's composition that will be made of asymmetry aromatic tetracarboxylic acid or 15～55 moles of % of its ester and symmetry aromatic tetracarboxylic acid or 85～45 moles of % of its ester and aromatic diamine composition mix the formed mixing solutions that is essentially free state with equimolar amount roughly, be configured as pipe with the spinning-shaping method, carry out heat treated, imidization.
(5) a kind of manufacture method of semi-conductivity endless tubular polyimide film, it is characterized in that, the aromatic tetracarboxylic acid's composition that constitutes by asymmetry aromatic tetracarboxylic acid or 15～55 moles of % of its ester and symmetry aromatic tetracarboxylic acid or 85～45 moles of % of its ester and aromatic diamine composition with the mixing solutions that is essentially free state that roughly equimolar amount mixes in, total with respect to aromatic tetracarboxylic acid's composition and aromatic diamine composition is measured 100 weight parts, the carbon black that disperses 1～35 weight part, the monomer mixture solution of formed semi-conductivity is configured as pipe with the spinning-shaping method, carry out heat treated, imidization.
(6) a kind of semi-conductivity endless tubular polyimide film of intermediate duplication band of the electrofax mode that is used for by (5) described manufacture method manufacturing.
B. second invention
In addition, the present inventor furthers investigate in order to solve above-mentioned problem, found that: heat treated aromatic tetracarboxylic acid's composition and aromatic diamine composition, make a part carry out polycondensation in fact and become the mixing solutions that contains aromatic amides acid oligomer (number-average molecular weight is about 1000～7000 aromatic amides acid) earlier, after being mixed in conductive carbon black in this mixing solutions, be rotated shaping, then, carry out imidization and handle the semi-conductivity endless tubular polyimide film that can obtain to have homogeneous resistivity thus.The present inventor finds based on this, by further development, thereby finishes the present invention (below be also referred to as " second invention ").
That is, second invention provides following semi-conductivity aromatic amides acid composition and manufacture method thereof and semi-conductivity endless tubular polyimide film and the manufacture method thereof of using this semi-conductivity aromatic amides acid composition.
(7) a kind of semi-conductivity aromatic amides acid composition, it is characterized in that, contain by the aromatic tetracarboxylic acid's composition more than 2 kinds and aromatic diamine and carry out aromatic amides acid oligomer, carbon black and the organic polar solvent that polycondensation was obtained with equimolar amount roughly.
(8) as (7) described semi-conductivity aromatic amides acid composition, it is characterized in that, above-mentioned aromatic amides acid oligomer is to carry out the aromatic amides acid oligomer that polycondensation was obtained under the temperature in organic polar solvent, below about 80 ℃ of equimolar amount roughly by the aromatic tetracarboxylic acid's dianhydride more than 2 kinds and aromatic diamine.
(9) as (8) described semi-conductivity aromatic amides acid composition, it is characterized in that, aromatic tetracarboxylic acid's dianhydride more than 2 kinds is by 15～55 moles of % of asymmetry aromatic tetracarboxylic acid dianhydride and 85～45 moles of mixtures that % constituted of symmetry aromatic tetracarboxylic acid dianhydride.
(10) as (7) described semi-conductivity aromatic amides acid composition, it is characterized in that, above-mentioned aromatic amides acid oligomer is to carry out the aromatic amides acid oligomer that polycondensation was obtained by the aromatic tetracarboxylic acid's diester more than 2 kinds and aromatic diamine with equimolar amount roughly in organic polar solvent, under the temperature about 90～120 ℃.
(11) as (10) described semi-conductivity aromatic amides acid composition, it is characterized in that, aromatic tetracarboxylic acid's diester more than 2 kinds is by 15～55 moles of % of asymmetry aromatic tetracarboxylic acid diester and 85～45 moles of mixtures that % constituted of symmetry aromatic tetracarboxylic acid diester.
As (7) described semi-conductivity aromatic amides acid composition, it is characterized in that (12) number-average molecular weight of above-mentioned aromatic amides acid oligomer is about 1000～7000.
As (7) described semi-conductivity aromatic amides acid composition, it is characterized in that (13) measure 100 weight parts with respect to the total of aromatic tetracarboxylic acid's composition and organic diamine, the sooty use level is about 3～30 weight parts.
(14) a kind of manufacture method of semi-conductivity endless tubular polyimide film is characterized in that, (7) described semi-conductivity aromatic amides acid composition is rotated shaping, heat treated.
(15) a kind of semi-conductivity endless tubular polyimide film of intermediate duplication band of the electrofax mode that is used for by (14) described manufacture method manufacturing.
(16) a kind of manufacture method of semi-conductivity aromatic amides acid composition, it is characterized in that, in organic polar solvent, aromatic tetracarboxylic acid's composition more than 2 kinds and aromatic diamine carry out the part polycondensation with equimolar amount roughly, become aromatic amides acid oligomer solution, with this aromatic amides acid oligomer solution and conductive carbon black powder uniform mixing.
C. the 3rd invention
The present inventor furthers investigate in order to solve above-mentioned problem, found that: in organic polar solvent with aromatic tetracarboxylic acid diester and the aromatic diamine and become nylon salt type monomer solution of the dissolving of equimolar amount roughly more than 2 kinds, the mixing solutions that mixes the high molecular polyimide precursor solution of regulation or high-molecular weight polyamidoimide solution and obtain in this nylon salt type monomer solution is being excellent aspect the sooty dispersion stabilization.And find: be rotated shaping by using the semiconductive polyimide class precursor composition that above-mentioned mixing solutions and carbon black uniform mixing are formed, then imidization is handled, the semi-conductivity endless tubular polyimide class film that can obtain to have homogeneous resistivity.The present inventor is by further development, thereby finishes the present invention (below be also referred to as " the 3rd invention ").
That is, the 3rd invention provides following semiconductive polyimide class precursor composition and manufacture method thereof, and semi-conductivity endless tubular polyimide class film and the manufacture method thereof of using this semiconductive polyimide class precursor composition.
(17) a kind of semiconductive polyimide class precursor composition, it is characterized in that, aromatic tetracarboxylic acid's diester more than 2 kinds and aromatic diamine are being dissolved in the nylon salt type monomer solution that forms in the organic polar solvent with equimolar amount roughly, mix high-molecular weight polyimide precursor solution or high-molecular weight polyamidoimide solution, the modulation mixing solutions is dispersed in carbon black in this mixing solutions.
(18) as (17) described semiconductive polyimide class precursor composition, it is characterized in that, aromatic tetracarboxylic acid's diester more than 2 kinds is by 10～55 moles of % of asymmetry aromatic tetracarboxylic acid diester and 90～45 moles of mixtures that % constituted of symmetry aromatic tetracarboxylic acid diester.
(19) as the described semiconductive polyimide class of claim (17) precursor composition, it is characterized in that, aromatic tetracarboxylic acid's diester more than 2 kinds, be by 2,3,3 ' of asymmetry, 10～55 moles of % of 4 '-biphenyltetracarboxyacid acid diester and symmetric 3,3 ', 4,90～45 moles of mixtures that % constituted of 4 '-biphenyltetracarboxyacid acid diester.
(20) as (17) described semiconductive polyimide class precursor composition, it is characterized in that, the high-molecular weight polyimide precursor solution is that number-average molecular weight is the polyamic acid solution more than 10000, and high-molecular weight polyamidoimide solution is that number-average molecular weight is the polyamidoimide solution more than 10000.
(21) as the described semiconductive polyimide class of claim (20) precursor composition, it is characterized in that, above-mentioned number-average molecular weight is the polyamic acid solution more than 10000, reacts manufacturing by biphenyl tetracarboxylic dianhydride and diaminodiphenyl oxide with equimolar amount roughly in organic polar solvent.
(22) as (20) described semiconductive polyimide class precursor composition, it is characterized in that, described number-average molecular weight is the polyamidoimide solution more than 10000, reacts manufacturing by trimellitic acid 1,2-anhydride and the formed acid anhydrides of benzophenone tetracarboxylic dianhydride and aromatic isocyanate with equimolar amount roughly in organic polar solvent.
(23) a kind of manufacture method of semi-conductivity endless tubular polyimide class film is characterized in that, (17) described semiconductive polyimide class precursor composition is configured as pipe with the spinning-shaping method, carries out heat treated, imidization.
(24) a kind of surface resistivity by (23) described manufacture method manufacturing is 10 7～10 14Ω/, be used for the semi-conductivity endless tubular polyimide class film of the intermediate duplication band of electrofax mode.
(25) a kind of manufacture method of semiconductive polyimide class precursor composition, it is characterized in that, aromatic tetracarboxylic acid's diester more than 2 kinds and aromatic diamine are being dissolved in the nylon salt type monomer solution that forms in the organic polar solvent with equimolar amount roughly, mix high-molecular weight polyimide precursor solution or high-molecular weight polyamidoimide solution, the modulation mixing solutions is dispersed in carbon black in this mixing solutions.
D. the 4th invention
The present inventor furthers investigate in order to solve above-mentioned problem, found that: carbon black is being dispersed in the carbon black dispersion liquid that forms in the organic polar solvent, with dissolving aromatic tetracarboxylic acid's diester of equimolar amount roughly and aromatic diamine, can modulate the semi-conductivity high density polyimide precursor composition of dispersity of carbon black excellence thus.And find: be rotated shapings, then carry out imidization processing, the semi-conductivity endless tubular polyimide film that can obtain to have homogeneous resistivity by using semi-conductivity high density polyimide precursor composition.The present inventor is by further development, thereby finishes the present invention (below be also referred to as " the 4th invention ")
That is, the 4th invention provides following semi-conductivity high density polyimide precursor composition and manufacture method thereof, and semi-conductivity endless tubular polyimide film and the manufacture method thereof of using this semi-conductivity high density polyimide precursor composition.
(26) a kind of manufacture method of semi-conductivity high density polyimide precursor composition, it is characterized in that, carbon black is being dispersed in the carbon black dispersion liquid that forms in the organic polar solvent, with dissolving aromatic tetracarboxylic acid's diester of equimolar amount roughly and aromatic diamine.
(27) as the manufacture method of (26) described semi-conductivity high density polyimide precursor composition, it is characterized in that, aromatic tetracarboxylic acid's diester is by 10～55 moles of % of asymmetry aromatic tetracarboxylic acid diester and 90～45 moles of mixtures that % constituted of symmetry aromatic tetracarboxylic acid diester.
(28) as the manufacture method of (26) described semi-conductivity high density polyimide precursor composition, it is characterized in that, aromatic tetracarboxylic acid's diester, be by 2,3,3 ' of asymmetry, 10～55 moles of % of 4 '-biphenyltetracarboxyacid acid diester and symmetric 3,3 ', 4,90～45 moles of mixtures that % constituted of 4 '-biphenyltetracarboxyacid acid diester.
(29) as the manufacture method of (26) described semi-conductivity high density polyimide precursor composition, it is characterized in that, measure 100 weight parts with respect to the total of aromatic tetracarboxylic acid's diester and aromatic diamine, carbon black is about 5～35 weight parts.
(30) a kind of semi-conductivity high density polyimide precursor composition by (26) described manufacture method manufacturing.
(31) a kind of manufacture method of semi-conductivity endless tubular polyimide film is characterized in that, (30) described semi-conductivity high density polyimide precursor composition is configured as pipe with the spinning-shaping method, carries out heat treated, imidization.
(32) a kind of surface resistivity by (31) described manufacture method manufacturing is 10 7～10 14The semi-conductivity endless tubular polyimide film of the intermediate duplication band of the electrofax mode that is used for of Ω/.
Embodiment
Below, the present invention is divided into " A. first invention ", " B. second invention ", " C. the 3rd invention " and " D. the 4th invents " does detailed explanation.
A. first invention
A-1. endless tubular polyimide film
Endless tubular polyimide film of the present invention (below be also referred to as " tubulose PI film "), with specific aromatic tetracarboxylic acid's composition and aromatic diamine composition as shaping raw material.Specifically, non-conductive tubulose PI film of the present invention with specific aromatic tetracarboxylic acid's composition and aromatic diamine composition as shaping raw material, in addition, semi-conductivity tubulose PI film of the present invention, except above-mentioned shaping raw material, be raw material also with the carbon black of specified amount (below be also referred to as " CB ") in order to give electroconductibility.
Aromatic tetracarboxylic acid's composition
As aromatic tetracarboxylic acid's composition of shaping raw material, use the mixture of asymmetry aromatic tetracarboxylic acid composition (in asymmetry aromatic tetracarboxylic acid or its ester at least a) and symmetry aromatic tetracarboxylic acid composition (in symmetry aromatic tetracarboxylic acid or its ester at least a).
So-called asymmetry aromatic tetracarboxylic acid can enumerate on monocycle or polycyclic aromatic nucleus (phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, anthracene nucleus), and 4 carboxyls are bonded to the compound on the non-point symmetry position, perhaps 2 monocycle aromatic nucleus (phenyl ring) with-CO-,-CH 2-,-SO 2-waiting on the crosslinked compound of base or singly-bound, 4 carboxyls are bonded to the compound on the non-point symmetry position.
As asymmetry aromatic tetracarboxylic acid's object lesson, can enumerate 1,2,3,4-benzene tertacarbonic acid, 1,2,6,7-naphthalene tetracarboxylic acid, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4 '-benzophenone tetracarboxylic acid, 2,3,3 ', 4 '-phenyl ether tetracarboxylic acid, 2,3,3 ', 4 '-ditan tetracarboxylic acid, 2,3,3 ', 4 '-diphenylsulfone acid etc.
As asymmetry aromatic tetracarboxylic acid's ester used in the present invention, can enumerate above-mentioned asymmetry aromatic tetracarboxylic acid's diester (half ester), specifically, can enumerate an esterified compound that among 4 carboxylic acids of above-mentioned asymmetry tetracarboxylic acid, has in 2 adjacent on the esterified and aromatic nucleus of 2 carboxyls carboxyls.
As 2 esters among above-mentioned asymmetry aromatic tetracarboxylic acid's diester, can enumerate two lower alkyl esters, two C such as preferred dimethyl ester, diethyl ester, dipropyl 1-3Alkyl ester (particularly dimethyl ester).
Among above-mentioned asymmetry aromatic tetracarboxylic acid's diester, preferably use 2,3,3 ', 4 '-biphenyltetracarboxyacid acid dimethyl ester, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid diethyl ester especially preferably uses 2,3,3 ', 4 '-biphenyltetracarboxyacid acid dimethyl ester.
In addition, above-mentioned asymmetry aromatic tetracarboxylic acid's diester can adopt commercially available or with the known method manufacturing.For example, by making the corresponding alcohol of 1 part of corresponding asymmetry aromatic tetracarboxylic acid's dianhydride and 2 parts (mol ratio) (lower alcohol, preferred C 1-3Alcohol etc.) known method such as reaction can be made at an easy rate.By such method, open loop just can be manufactured on the diester (half ester) that has ester group and carboxyl on the adjacent carbon on the aromatic nucleus respectively with the alcohol reaction as the acid anhydrides of raw material.
So-called symmetry aromatic tetracarboxylic acid, can enumerate at monocycle or polycyclic aromatic nucleus (phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, anthracene nucleus) go up, 4 carboxyls are bonded to the compound on the point symmetry position, perhaps 2 monocycle aromatic nucleus (phenyl ring etc.) with-CO-,-O-,-CH 2-,-SO 2-wait on the crosslinked compound of base or singly-bound, 4 carboxyls are bonded to the compound on the point symmetry position.
As symmetry aromatic tetracarboxylic acid's object lesson, can enumerate 1,2,4,5-benzene tertacarbonic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-phenyl ether tetracarboxylic acid, 3,3 ', 4,4 '-ditan tetracarboxylic acid, 3,3 ', 4,4 '-diphenylsulfone acid etc.
As symmetry aromatic tetracarboxylic acid's ester used in the present invention, can enumerate above-mentioned symmetry aromatic tetracarboxylic acid's diester (half ester), specifically, can enumerate an esterified compound that among 4 carboxylic acids of above-mentioned symmetry tetracarboxylic acid, has in 2 adjacent on the esterified and aromatic nucleus of 2 carboxyls carboxyls.
As 2 esters among above-mentioned symmetry aromatic tetracarboxylic acid's diester, can enumerate two lower alkyl esters, C such as preferred dimethyl ester, diethyl ester, dipropyl 1-3Alkyl ester (particularly dimethyl ester).
Among above-mentioned symmetry aromatic carboxylic acid diester, preferably use 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dimethyl ester, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid diethyl ester, 2,3,5,6-benzene tertacarbonic acid dimethyl ester especially preferably uses 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dimethyl ester.
In addition, above-mentioned symmetry aromatic tetracarboxylic acid's diester can adopt commercially available or with the known method manufacturing.For example, by making the corresponding alcohol of 1 part of corresponding symmetry aromatic tetracarboxylic acid's dianhydride and 2 parts (mol ratio) (lower alcohol, preferred C 1-3Alcohol etc.) known method such as reaction can be made at an easy rate.By such method, open loop just can be manufactured on the diester (half ester) that has ester group and carboxyl on the adjacent carbon on the aromatic nucleus respectively with the alcohol reaction as the acid anhydrides of raw material.
The ratio of mixture of asymmetry and symmetric aromatic tetracarboxylic acid or its ester, special stipulation is, asymmetry aromatic tetracarboxylic acid or its ester are about 15～55 moles of % (preferred 20～50 moles of %), and symmetry aromatic tetracarboxylic acid or its ester are about 85～45 moles of % (preferred 80～50 moles of %).Particularly, asymmetry aromatic tetracarboxylic acid's diester is about 20～50 moles of %, and symmetry aromatic tetracarboxylic acid's diester is about 80～50 moles of %, is preferred the use.
Why must cooperate above-mentioned asymmetry and symmetric aromatic tetracarboxylic acid's composition, the reasons are as follows.When only utilizing symmetry aromatic tetracarboxylic acid or its ester, because polyimide film shows crystallinity, so overlay film efflorescence and can't carry out membranization in heat treated.On the other hand, when only utilizing asymmetry aromatic tetracarboxylic acid or its ester, though can be configured as endless tubular PI film, but a little less than the yield strength and spring rate of this film that is obtained, when using as rotating band, bad response in driving not only, and the stage rotates problems such as band elongation in the early stage.
Relative therewith, if use aromatic tetracarboxylic acid or its ester that constitutes by above-mentioned ratio of mixture, then can obtain high system film (plasticity), and can obtain to have the semi-conductivity endless tubular PI film of high-yield strength and snappiness rate.
In addition, the applicant thinks, by adding asymmetry aromatic tetracarboxylic acid or its ester, can make the bending of polyamic acid molecule, produces snappiness.
And the coexistence effect of the aromatic tetracarboxylic acid of above-mentioned symmetry and asymmetry or its ester can access performance most effectively when the two ratio of mixture as noted above.
The aromatic diamine composition
As the aromatic diamine composition, can enumerate the compound that on an aromatic nucleus (phenyl ring etc.), has 2 amino, perhaps the aromatic nucleus more than 2 (phenyl ring etc.) with-O-,-S-,-CO-,-CH 2-,-SO-,-SO 2-wait base or the crosslinked compound of singly-bound with 2 amino.Specifically, for example, p-penylene diamines, o-penylene diamines, m-penylene diamines, 4,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino, two phenylcarbamoyls, 4,4 '-diaminodiphenylmethane, 1, two (4-amino-benzene oxygen) benzene of 4-etc.Wherein, preferred especially 4,4 '-diaminodiphenyl oxide.This is because by using these aromatic diamine compositions, reaction can be carried out more smoothly, simultaneously, can make more tough and has the more film of high heat resistance.
Organic polar solvent
Organic polar solvent as the mixing solutions that is used for being essentially free state, preferably proton there is inertia class organic polar solvent, for example, use N-N-methyl-2-2-pyrrolidone N-(hereinafter referred to as " NMP "), N, dinethylformamide, N, N-diethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, 1,3-dimethyl-2-imidazolone etc.It can be one or more mixing solutions wherein.Preferred especially NMP.The usage quantity of organic polar solvent, with respect to measuring 100 weight parts as the aromatic tetracarboxylic acid's composition of raw material and the total of aromatic diamine composition, be that (about preferred 80～230 weight parts, more preferably about 100～200 weight parts) get final product about 65～300 weight parts.
Carbon black (CB)
When making semi-conductivity tubulose PI film of the present invention, except above-mentioned each composition, also use the CB powder in order to give resistance characteristic.Use the sooty reason to be, compare with other the metal known to usually and the electro-conductive material of metal oxide, with synthetic monomer mixture solution blended blending dispersion and stability (after the blending dispersion through time change) excellence, and polycondensation do not had detrimentally affect.
This CB powder differently has a multiple physical property (resistance, volatile matter, specific surface area, particle diameter, pH value, DBP oil number etc.) according to what it made raw material (Sweet natural gas, acetylene gas, tar etc.) and create conditions (combustion conditions).(this mostly is with the acetylene gas is the CB powder that raw material is made) of the conductive finger absolute altitude of structure prosperity, though the resistance that just can obtain to stipulate with more a spot of fill-up, blending dispersion is bad.Though the conduction index is not high, but the CB powder that the oxide treatment that the pH value is low is crossed, the CB powder that contains more volatile matter, though need many fillings just can reach regulation resistance, blending dispersion and storage stability excellence, and be easy to obtain to have the band of homogeneous resistance.
This electroconductibility CB powder, usually median size is about 15～65nm, under the situation especially for the intermediate duplication band of employed electrofax mode in color printer, color copy machine etc. etc., preferred median size is about 20～40nm.
For example, can enumerate furnace black that thermally oxidized black, oxide treatment cross etc.Specifically, Special Black 4 (pH3, volatile matter 14%, particle diameter 25nm), Special Black 5 (pH3, volatile matter 15%, particle diameter 20nm) etc. that can illustration Degusa corporate system.
The amount of the CB powder that is added, with respect to the mixing solutions that is essentially free state measure 100 weight parts as the aromatic tetracarboxylic acid's composition of shaping raw material and the total of aromatic diamine composition, preferably use (about preferred 5～25 weight parts) about 1～35 weight part.
Here, why in above-mentioned scope, use the CB powder, be for give to film be in semiconductor regions volume specific resistance (Ω cm) (VR) and surface resistivity (Ω/) (SR).Under more than being limited to about 1 weight part be because, in order to obtain competent electroconductibility, the amount of this degree is necessary; On below being limited to about 35 weight parts be because, show lower resistance, simultaneously, keep plasticity, prevent the low of film self physical property.
The modulation of monomer mixture solution
The quantitative aromatic tetracarboxylic acid's composition of hybrid regulatory, aromatic diamine composition and organic polar solvent, the mixing solutions that is essentially free state of modulation shaping usefulness (below be also referred to as " monomer mixture solution ").What is called of the present invention non-conductive tubulose PI film and semi-conductivity tubulose PI film only are the difference that the CB powder has or not, and as the monomer mixture solution of shaping raw material, the two is synthetic with identical condition.Its modulation order is not particularly limited.Aromatic tetracarboxylic acid's composition used in the present invention is different with the situation of using reactive high aromatic tetracarboxylic acid's dianhydride, do not react in fact down at low temperature (for example below 30～40 ℃) with two amine components, aspect the modulation monomer mixture solution also be favourable a bit.
Monomer mixture solution be above-mentioned aromatic tetracarboxylic acid's composition and aromatic diamine composition with the reaction of equimolar amount roughly than, mix and be dissolved in the organic polar solvent and synthetic.These compositions so be easy to be dissolved in the organic polar solvent, can make it with the high density uniform dissolution because be monomer, and the solution that is obtained can keep free state in fact.The present invention is that the mixing solutions with this free state uses as shaping raw material.
Here, what is called is equimolar amount roughly, is meant that the polycondensation of aromatic tetracarboxylic acid's composition and aromatic diamine composition is carried out smoothly, obtains the reaction ratio of the high-molecular weight polyimide of regulation.What is called is essentially free state, is meant that each composition all is a free state in mixing solutions, but the present invention is not being had in the dysgenic scope, also can contain the low molecule polycondensation thing of oligopolymer degree on a small quantity.
The usage quantity of organic polar solvent, with respect to measuring 100 weight parts as the aromatic tetracarboxylic acid's composition of raw material and the total of aromatic diamine composition, be that (about preferred 80～230 weight parts, more preferably about 100～200 weight parts) get final product about 65～300 weight parts.Because the mixing solutions that is essentially free state of manufacturing is easy to be dissolved in the above-mentioned organic polar solvent, so have the advantage of the amount that can do one's utmost to reduce employed solvent.
Below, the modulator approach of illustration monomer mixture solution.
As the 1st example, at first, with aromatic tetracarboxylic acid's composition mixed dissolution of the symmetry of afore mentioned rules mole % and asymmetry in organic polar solvent.Be equimolar aromatic diamine composition roughly while stirring in this solution to add, after the uniform dissolution, become the monomer mixture solution of shaping usefulness with respect to aromatic tetracarboxylic acid's composition.
As the 2nd example, modulate solution that constitutes by symmetry aromatic tetracarboxylic acid's composition of afore mentioned rules amount and roughly equimolar with it aromatic diamine composition and the solution that constitutes by asymmetry aromatic tetracarboxylic acid's composition of specified amount and roughly equimolar with it aromatic diamine composition respectively.Mix this solution separately, make that 2 kinds of aromatic tetracarboxylic acid's compositions are the mole % of regulation, become the monomer mixture solution of shaping usefulness.
As the 3rd example, in organic polar solvent, add the symmetry of specified amount and the aromatic tetracarboxylic acid's composition and the aromatic diamine composition of asymmetry separately simultaneously, modulate uniform monomer mixture solution.
The existing polyimide acid solution can only reach 25 weight % at most, and is relative therewith, and the non-volatile content in the monomer mixture solution of the present invention can reach the high density of (particularly 30～45 weight %) about 45 weight %.What is called as used in this specification " non-volatile content concentration " is meant the concentration that the method put down in writing by embodiment is measured.By using the monomer mixture solution of high density, polycondensation is promptly carried out, and can realize the shortening of curring time.In addition, can easily make the thicker film of film, because employed quantity of solvent is few, so can suppress cost and the evaporation of solvent is removed to become easy.
In addition, in the scope that effect of the present invention is had no adverse effects, also can in above-mentioned monomer mixture solution, add glyoxaline compound (glyoxal ethyline, 1,2 dimethylimidazole, 2-methyl-4-methylimidazole, 2-ethyl-4-ethyl imidazol(e), 2-phenylimidazole), tensio-active agent additives such as (fluorine class tensio-active agents etc.).
In the manufacturing of semiconduction tubulose PI film, adopt monomer mixture solution with the semi-conductivity of carbon black dispersion in monomer mixture solution.The blending means of mixed C B powder in monomer mixture solution, known method such as employing stirring get final product, and are not particularly limited.When carrying out this stirring, use ball mill better, so just can obtain the semi-conductivity monomer mixture solution of the shaping usefulness that CB is evenly dispersed.
The sooty usage quantity as mentioned above, is measured 100 weight parts with respect to the total of aromatic tetracarboxylic acid's composition and aromatic diamine composition, uses 1～35 weight part, preferred 5～25 weight parts.
A-2. the manufacture method of endless tubular polyimide film
Next, the manufacturing process to the tubulose PI film of the monomer mixture solution that uses above-mentioned synthetic monomer mixture solution or semi-conductivity is illustrated.Below, the manufacturing process that uses monomer mixture solution is illustrated, and uses the manufacturing process of semi-conductivity monomer mixture solution also can implement equally.
This manufacturing process adopts the method for rotary forming that uses rotor (drum).At first monomer mixture solution is injected the inner face of rotor, evenly curtain coating is all in inner face.
The method of injection-curtain coating is, for example, in the rotor that stops, injecting after the monomer mixture solution that obtains final film thickness institute a great deal of, slowly improves speed of rotation, and is up to the speed that centrifugal force works, all in inner face by the even curtain coating of centrifugal force.Perhaps, injection-curtain coating does not use centrifugal force passable yet.For example, the slot-shaped nozzle in that the inner face configuration of cylinder is grown crosswise continues this cylinder of rotation lentamente, and this nozzle (with than this speed of rotation faster speed) also rotates.Then, the monomer mixture solution with shaping usefulness all sprays to this cylinder inner face equably from this nozzle.This cylinder mounting is on the rotation roller, and the rotation by this roller can be rotated indirectly.
Heating is the indirect heating that disposes thermal source such as far infra-red heater for example around this cylinder, carry out from the outside.The size of this cylinder depends on the size of desirable semiconduction tubulose PI film.
Heating slowly heats up the cylinder inner face, at first is about 100～190 ℃, preferably reaches (the 1st heating phase) about 110～130 ℃.Heat-up rate for example gets final product about 1～2 ℃/min.Kept under said temperature 30～120 minutes, and made only about half of above solvent evaporates, being shaped has self-supportive tubular film.In order to carry out imidization, need reach the temperature more than 280 ℃, but if heat with high like this temperature just beginning most, then not only polyimide shows high crystallization, influence the dispersion state of CB, and existence can't form tough problems such as overlay film.Therefore, as the 1st heating phase, ceiling temperature is the highest to be controlled at about 190 ℃, stops polycondensation under this temperature, just obtains tough tubulose PI film.
If next this stage, as the 2nd heating phase, heats in order to finish imidization after finishing, its temperature is (preferred about 300～380 ℃) about 280～400 ℃.At this moment neither reach this temperature suddenly from the temperature of the 1st heating phase, to reach this temperature better but slowly heat up.
In addition, the 2nd heating phase, can be directly under being attached to the state of rotor inner face, the endless tubular film carries out, also can after the 1st heating phase finished, the endless tubular film be peeled off taking-up from rotor, other heater means that is used to reach imidization is provided, is heated to 280～400 ℃.The used time of this imidization, be about usually about 2～3 hours.Therefore, the used time of the 1st and the 2nd whole operations of heating phase, be generally about 4～7 hours.
So just made non-conductive (or semi-conductivity) of the present invention PI film.Though there is no particular limitation for the thickness of this film, be generally about 30～200 μ m, be preferably about 60～120 μ m.Particularly, when being used as the intermediate duplication band of electrofax mode, be preferably about 75～100 μ m.
Under the situation that is semi-conductivity PI film, the semi-conductivity of this film be by volume specific resistance (Ω cm) (VR) and surface resistivity (resistance characteristic of the two common decision of Ω/) (SR), this characteristic is to give by the blending dispersion of CB powder.And the scope of this resistance, can freely change by the combined amount of CB powder basically.As the electrical resistivity range of film of the present invention, can illustratively be VR:10 2～10 14, SR:10 3～10 15,, can illustratively be VR:10 as preferable range 6～10 13, SR:10 7～10 14These electrical resistivity range can reach at an easy rate by the use level that adopts above-mentioned CB powder.In addition, the CB content in the film of the present invention is generally about 5～25 weight %, about preferred 8～20 weight %.
Semi-conductivity PI film of the present invention has the very resistivity of homogeneous.That is, the unique point of semi-conductivity PI film of the present invention is, the variability of the logarithm conversion value of surface resistivity SR and volume specific resistance VR is little, and in film in the full measuring point, the standard deviation of logarithm conversion value separately is in 0.2, in preferred 0.15.In addition, have the little such feature of difference of the surface resistivity (logarithm conversion value) at the film surface and the back side, this difference is in 0.4, preferably in 0.2.And possess following feature: the logarithm conversion value LogSR of surface resistivity deducts the value of the logarithm conversion value LogVR of volume specific resistance, can maintain 1.0～3.0, preferred 1.5～3.0 such high values.
Semi-conductivity PI film of the present invention, because its excellent function such as resistance characteristic, so serve many purposes.For example, as the important use that needs charged characteristic, can enumerate the intermediate duplication band of the electrofax mode that is used for color printer, color copy machine etc. etc.As this band, necessary semi-conductivity (resistivity) for example is that VR is 10 9～10 12, SR is 10 10～10 13, can use semi-conductivity endless tubular PI film of the present invention with being well suited for.
Non-conductive or semi-conductivity PI film of the present invention, the excellent performance as band has high yield strength (σ Y) and breaking tenacity (σ Cr).Yield strength (σ Y) more than 120MPa, 120～160MPa particularly, the ratio (σ of breaking tenacity and yield strength Cr/ σ Y) more than 1.10, particularly about 1.10～1.35.
B. second invention
Semi-conductivity endless tubular polyimide film of the present invention (below be also referred to as " semi-conductivity tubulose PI film "), be the semi-conductivity aromatic amides acid composition that will contain aromatic amides acid oligomer, conductive carbon black (below be also referred to as " CB ") and organic polar solvent, handle by spinning-shaping, amidation and make.
B-1. semi-conductivity aromatic amides acid composition
Semi-conductivity aromatic amides acid composition of the present invention, be in organic polar solvent, aromatic tetracarboxylic acid's composition more than 2 kinds and aromatic diamine composition are carried out the part polycondensation and become aromatic amides acid oligomer (the aromatic amides acid of number-average molecular weight about 1000～7000) solution with equimolar amount roughly, again with this solution and conductive carbon black powder uniform mixing and synthetic.
(1) aromatic tetracarboxylic acid's composition
As the aromatic tetracarboxylic acid's composition more than 2 kinds of shaping raw material, use the mixture of at least a asymmetry aromatic tetracarboxylic acid's derivative and at least a symmetry aromatic tetracarboxylic acid's derivative.
Asymmetry aromatic tetracarboxylic acid's derivative
In the present invention, as asymmetry aromatic tetracarboxylic acid derivative, can enumerate asymmetry aromatic tetracarboxylic acid dianhydride or asymmetry aromatic tetracarboxylic acid diester (half ester).
Here, so-called asymmetry aromatic tetracarboxylic acid, can enumerate on monocycle or polycyclic aromatic nucleus (phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, anthracene nucleus), 4 carboxyls are bonded to the compound on the non-point symmetry position, perhaps 2 monocycle aromatic nucleus (phenyl ring etc.) with-CO-,-CH 2-,-SO 2-waiting on the crosslinked compound of base or singly-bound, 4 carboxyls are bonded to the compound on the non-point symmetry position.
As asymmetry aromatic tetracarboxylic acid's object lesson, can enumerate 1,2,3,4-benzene tertacarbonic acid, 1,2,6,7-naphthalene tetracarboxylic acid, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4 '-benzophenone tetracarboxylic acid, 2,3,3 ', 4 '-phenyl ether tetracarboxylic acid, 2,3,3 ', 4 '-ditan tetracarboxylic acid, 2,3,3 ', 4 '-diphenylsulfone acid etc.
As asymmetry aromatic tetracarboxylic acid's dianhydride used in the present invention, can enumerate above-mentioned asymmetry aromatic tetracarboxylic acid's dianhydride, specifically, can enumerate the compound that carboxyl adjacent in above-mentioned asymmetry tetracarboxylic acid, on the aromatic nucleus forms 2 acid anhydrides each other.Wherein, preferably use 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 1,2,6,7-naphthalene tetracarboxylic acid dianhydrides etc. especially preferably use 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride.
As asymmetry aromatic tetracarboxylic acid's diester used in the present invention (half ester), can enumerate above-mentioned asymmetry aromatic tetracarboxylic acid's diester (half ester), specifically, can enumerate an esterified compound that among 4 carboxylic acids of above-mentioned asymmetry tetracarboxylic acid, has in 2 adjacent on the esterified and aromatic nucleus of 2 carboxyls carboxyls.
As 2 esters in above-mentioned asymmetry aromatic tetracarboxylic acid's diester, can enumerate two or two lower alkyl esters, two C such as preferred dimethyl ester, diethyl ester, dipropyl 1-3Alkyl ester (particularly dimethyl ester).
Among above-mentioned symmetry aromatic carboxylic acid diester, preferably use 2,3,3 ', 4 '-biphenyltetracarboxyacid acid dimethyl ester, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid diethyl ester especially preferably uses 2,3,3 ', 4 '-biphenyltetracarboxyacid acid dimethyl ester.
In addition, above-mentioned asymmetry aromatic tetracarboxylic acid's diester can adopt commercially available or with the known method manufacturing.For example, by making the corresponding alcohol of 1 part of corresponding asymmetry aromatic tetracarboxylic acid's two dianhydride and 2 parts (mol ratio) (lower alcohol, preferred C 1-3Alcohol etc.) known method such as reacting can make at an easy rate.By such method, open loop just can be manufactured on the diester (half ester) that has ester group and carboxyl on the adjacent carbon of aromatic nucleus respectively with the alcohol reaction as the acid anhydrides of raw material.
Symmetry aromatic tetracarboxylic acid's derivative
In the present invention, as symmetry aromatic tetracarboxylic acid derivative, can enumerate symmetry aromatic tetracarboxylic acid dianhydride or symmetry aromatic tetracarboxylic acid diester (half ester).
Here, so-called symmetry aromatic tetracarboxylic acid, can enumerate on monocycle or polycyclic aromatic nucleus (phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, anthracene nucleus), 4 carboxyls are bonded to the compound on the point symmetry position, perhaps 2 monocycle aromatic nucleus (phenyl ring etc.) with-CO-,-O-,-CH 2-,-SO 2-wait on the crosslinked compound of base or singly-bound 4 carboxyls to be bonded to compound on the point symmetry position.
As symmetry aromatic tetracarboxylic acid's object lesson, can enumerate 1,2,4,5-benzene tertacarbonic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-phenyl ether tetracarboxylic acid, 3,3 ', 4,4 '-ditan tetracarboxylic acid, 3,3 ', 4,4 '-diphenylsulfone acid etc.
As symmetry aromatic tetracarboxylic acid's dianhydride used in the present invention, can enumerate above-mentioned symmetry aromatic tetracarboxylic acid's dianhydride, specifically, can enumerate in above-mentioned symmetry tetracarboxylic acid, adjacent carboxyl forms the compound of 2 acid anhydrides each other.Wherein, preferably use 1,2,4,5-benzene tertacarbonic acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride especially preferably uses 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride.This is owing to can play good effect to the film that is obtained at aspects such as intensity formation.
As symmetry tetracarboxylic acid diester used in the present invention (half ester), can enumerate above-mentioned asymmetry aromatic tetracarboxylic acid's diester (half ester), specifically, can enumerate an esterified compound that among 4 carboxylic acids of above-mentioned symmetry tetracarboxylic acid, has in 2 adjacent on the esterified and aromatic nucleus of 2 carboxyls carboxyls.
As 2 esters in above-mentioned symmetry aromatic tetracarboxylic acid's diester, can enumerate two lower alkyl esters, C such as preferred dimethyl ester, diethyl ester, dipropyl 1-3Alkyl ester (particularly dimethyl ester).
Among above-mentioned symmetry aromatic carboxylic acid diester, preferably use 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dimethyl ester, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid diethyl ester, 2,3,5,6-benzene tertacarbonic acid dimethyl ester especially preferably uses 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dimethyl ester.
In addition, above-mentioned symmetry aromatic tetracarboxylic acid's diester can adopt commercially available or with the known method manufacturing.For example, by making the corresponding alcohol of 1 part of corresponding symmetry aromatic tetracarboxylic acid's dianhydride and 2 parts (mol ratio) (lower alcohol, preferred C 1-3Alcohol etc.) known method such as reacting can make at an easy rate.By such method, open loop just can be manufactured on the diester (half ester) that has ester group and carboxyl on the adjacent carbon of aromatic nucleus respectively with the alcohol reaction as the acid anhydrides of raw material.
Ratio of mixture
The ratio of mixture of asymmetry and symmetric aromatic tetracarboxylic acid's derivative, special stipulation is, asymmetry aromatic tetracarboxylic acid's derivative is 10～55 moles of % (preferred 15～55 moles of %, more preferably 20～50 moles of %) about, symmetry aromatic tetracarboxylic acid's derivative is about 90～45 moles of % (preferred 85～45 moles of %, more preferably 80～50 moles of %).Particularly asymmetry aromatic tetracarboxylic acid dianhydride is about 20～50 moles of %, and symmetry aromatic tetracarboxylic acid's dianhydride is to use about 80～50 moles of % to be well suited for.
Why must cooperate aromatic tetracarboxylic acid's composition of above-mentioned symmetry and asymmetry, the reasons are as follows.When only utilizing symmetry aromatic tetracarboxylic acid derivative, because polyimide film shows crystallinity, so overlay film efflorescence and can't carry out membranization in heat treated.On the other hand, when only utilizing asymmetry aromatic tetracarboxylic acid derivative, though can be configured as endless tubular PI film, but a little less than the yield strength and spring rate of this film that is obtained, when using as rotating band, bad response in driving not only, and the stage rotates problems such as band elongation in the early stage.
Relative therewith, if use the aromatic tetracarboxylic acid's derivative that constitutes by above-mentioned ratio of mixture, then can obtain high system film (plasticity), and can obtain to have the semi-conductivity endless tubular PI film of high-yield strength and snappiness rate.
In addition, the applicant thinks, by adding asymmetry aromatic tetracarboxylic acid derivative, can make the bending of polyamic acid molecule, produces snappiness.
And the coexistence effect of aromatic tetracarboxylic acid's derivative of above-mentioned symmetry and asymmetry can access performance most effectively when the two ratio of mixture as noted above.
(2) aromatic diamine
As aromatic diamine, can enumerate the compound that on an aromatic nucleus (phenyl ring etc.), has 2 amino, perhaps the aromatic nucleus more than 2 (phenyl ring etc.) with-O-,-S-,-CO-,-CH 2-,-SO-,-SO 2-wait base or the crosslinked compound of singly-bound with 2 amino.Specifically, for example, p-penylene diamines, o-penylene diamines, m-penylene diamines, 4,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino, two phenylcarbamoyls, 4,4 '-diaminodiphenylmethane, 1, two (4-amino-benzene oxygen) benzene of 4-etc.Wherein, preferred especially 4,4 '-diaminodiphenyl oxide.This is because by using these aromatic diamine compositions, in more smooth the carrying out of reaction, can make more tough and has the more film of high heat resistance.
(3) organic polar solvent
As employed organic polar solvent, preferably proton there is inertia class organic polar solvent, for example, use N-N-methyl-2-2-pyrrolidone N-(hereinafter referred to as " NMP "), N, dinethylformamide, N, N-diethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, 1,3-dimethyl-2-imidazolone etc.The mixed solvent of wherein one or more all can.Preferred especially NMP.The usage quantity of organic polar solvent with respect to measuring 100 weight parts as the aromatic tetracarboxylic acid's composition of raw material and the total of aromatic diamine composition, is that (about preferred 150～250 weight parts) get final product about 100～300 weight parts.Because the aromatic amides acid oligomer of manufacturing is easy to be dissolved in the above-mentioned organic polar solvent, has the advantage that to do one's utmost to reduce employed quantity of solvent.
(4) modulation of aromatic amides acid oligomer solution
Following illustration is carried out above-mentioned mixed aromatic tetracarboxylic acid composition and organic diamine composition more than 2 kinds the part polycondensation and is modulated the method for aromatic amides acid oligomer (about number-average molecular weight 1000～7000) in organic polar solvent.
Modulator approach as the 1st kind of aromatic amides acid oligomer, by with the aromatic tetracarboxylic acid's dianhydride more than 2 kinds and aromatic diamine to carry out polycondensation under equimolar amount roughly, the temperature in organic polar solvent and below about 80 ℃, just can make aromatic amides acid oligomer (about number-average molecular weight 1000～7000).
Specifically, the mixture that constituted about 15～55 moles of % of asymmetry aromatic tetracarboxylic acid dianhydride (preferred 20～50 moles of %) and about 85～45 moles of % of symmetry aromatic tetracarboxylic acid dianhydride (preferred 80～50 moles of %) is offered polycondensation.Organic polar solvent adopts aforesaid, preferred especially NMP.
Below why being made as temperature of reaction about 80 ℃, be imidization reaction to take place when forming the aromatic amides acid oligomer in order to be suppressed at.Preferred temperature of reaction is 30～70 ℃.Temperature of reaction then is easy to form polyimide by imidization reaction, so not preferred if surpass 80 ℃.The difference of reaction times according to temperature of reaction changes, and is generally about a few hours～72 hour.
In addition, the adjusting of the molecular weight of aromatic amides acid oligomer adopts known any method can.For example, can carry out very suitably by following method: aromatic tetracarboxylic acid's composition/aromatic diamine composition carries out polyreaction with mol ratio 0.5～0.95, form after the aromatic amides acid oligomer of regulation molecular weight, add aromatic tetracarboxylic acid's composition as required, make aromatic tetracarboxylic acid's composition/aromatic diamine composition for roughly waiting mole (with reference to special fair 1-22290 communique); At aromatic tetracarboxylic acid's composition/aromatic diamine composition during with reaction with same mole roughly, the compound that makes the such inhibition high molecular of water is with specified amount coexistence (with reference to special fair 2-3820 communique) etc.
Modulator approach as the 2nd kind of aromatic amides acid oligomer, by with the aromatic tetracarboxylic acid's diester more than 2 kinds and aromatic diamine with equimolar amount roughly, in organic polar solvent and under the temperature about 90～120 ℃, carry out polycondensation, just can make aromatic amides acid oligomer (about number-average molecular weight 1000～7000).
Specifically, the mixture that constituted about 15～55 moles of % of asymmetry aromatic tetracarboxylic acid diester (preferred 20～50 moles of %) and about 85～45 moles of % of symmetry aromatic tetracarboxylic acid diester (preferred 80～50 moles of %) is offered polycondensation.Organic polar solvent adopts aforesaid, preferred especially NMP.
In order to adjust the aromatic amides acid oligomer with desirable molecular weight, its temperature of reaction and reaction times are close association.Though Heating temperature is generally 90～120 ℃ and gets final product, when temperature of reaction is in high-temperature area,, preferably shorten the reaction times for growing amount (imidization rate) and the polymer that suppresses the imide body quantizes.In addition, heat treated is to be warming up to specified temperature gradually, reacts under specified temperature about 1～3 hour, and cooling gets final product then.For example, be warming up to 90～120 ℃ with about 1 hour～4 hours, reaction under this temperature about 30 minutes～2 hours, cooling got final product then.
Above-mentioned the 1st kind and the 2nd in the modulator approach, what is called is equimolar amount roughly, is meant the aromatic amides acid of oligopolymer degree that can modulation specifications and then obtains reaction ratio as the semi-conductivity tubulose PI film of purpose.In addition, two kinds of composition uniform dissolution in organic polar solvent the time, also can heated (for example, about 40～70 ℃) as required.
Can modulate aromatic amides acid oligomer solution by above-mentioned the 1st kind and the 2nd kind of modulator approach, make that its number-average molecular weight (Mn) is about 1000～7000 (preferred about 3000～7000).Meaning specific to this scope is, if number-average molecular weight below 1000 (promptly, monomer, about dimer), then can't obtain the effect of conductive characteristic, more than 7000, then the solubleness because of oligopolymer extremely reduces as if number-average molecular weight, solution generation gelation etc. and can't use (for example, with reference to comparative example B-1).In addition, with regard to number-average molecular weight, for example can measure by the method that embodiment put down in writing.
The number-average molecular weight (Mn) that is modulated to of the present invention is about 1000～7000 aromatic amides acid oligomer, usually and the ratio (Mw/Mn) of weight-average molecular weight (Mw) below 2.
By the aromatic amides acid oligomer solution of this heat treated manufacturing, principal constituent is the aromatic amides acid oligomer, further reacts product that imidization takes place etc. but also can contain its part.But the production rate of the imide body in the aromatic amides acid oligomer (imidization rate) is below 30%, preferably below 25%, more preferably below 20%.In addition, the growing amount of the imide body of by-product (imidization rate) for example, can be measured by the method that embodiment put down in writing.
In addition, can be high density about 30～45 weight % with the non-volatile content concentration adjustment in the aromatic amides acid oligomer solution.Why can modulate high like this non-volatile content concentration and be because, owing to be the oligopolymer of high molecular not, so be easy to be dissolved in the solvent.Therefore therefore, can easily make the thicker film of film, and employed quantity of solvent is few, can suppresses cost, and make solvent evaporation remove to become easy.In the employed what is called of this specification sheets " non-volatile content concentration ", be meant the concentration of measuring by the method for record in the Embodiment B-1.
(5) modulation of semi-conductivity aromatic amides acid composition
With such aromatic amides acid oligomer solution that obtains and electroconductibility CB powder uniform mixing, modulation semi-conductivity aromatic amides composition.
Use the reason of CB powder to be in order to give resistance characteristic, compare with electro-conductive materials such as other metal known to usually or metal oxides, with the monomer mixture solution that modulates blended blending dispersion and stability (after the blending dispersion through time change) excellence mutually, and polycondensation there is not detrimentally affect.
This CB powder differently has a multiple physical property (resistance, volatile matter, specific surface area, particle diameter, pH value, DBP oil number etc.) according to what it made raw material (Sweet natural gas, acetylene, tar etc.) and create conditions (combustion conditions).Even the CB powder of selecting a small amount of as far as possible blending dispersion, desirable resistance also can not produce deviation, stablize and obtain easily is better.
This electroconductibility CB powder, median size is about 15～65nm usually, particularly, when being used for the intermediate duplication band of employed electrofax modes such as color printer, color copy machine, preferred median size is about 20～40nm.
For example, can enumerate furnace black that thermally oxidized black, oxide treatment cross etc.Specifically, Special Black 4 (pH3, volatile matter 14%, particle diameter 25nm), Special Black 5 (pH3, volatile matter 15%, particle diameter 20nm) etc. that can illustration Degusa corporate system.
The CB powder is mixed in method in the aromatic amides acid oligomer solution,, then is not particularly limited if CB powder uniform mixing is scattered in method in the aromatic amides acid oligomer solution.For example, can use ball mill, simpson mill, ultrasonic wave shredder etc.
The amount of the CB powder that is added with respect to measuring 100 weight parts as the aromatic tetracarboxylic acid's composition of aromatic amides acid oligomer raw material and the total of organic diamine, is preferably used (more preferably about 10～25 weight parts) about 3～30 weight parts.
Here, why using the CB powder in above-mentioned scope, is volume specific resistance (VR) and the surface resistivity (SR) that is in semiconductor regions in order to give to film.Under be because in order to obtain competent electroconductibility, the amount of this degree is necessary more than being limited to about 3 weight parts; On be limited to about 30 weight parts be because, when showing lower resistance, keep plasticity, prevent the reduction of film self physical property.
Non-volatile content concentration in the semi-conductivity aromatic amides acid composition is about 30～45 weight %, the concentration of the CB powder in this non-volatile content is (about preferred 10～20 weight %) about 3～25 weight %, is (preferred 80～90 weight %) about 75～97 weight % from the concentration of the non-volatile content of aromatic amides acid oligomer.
In addition, in the scope that effect of the present invention is had no adverse effects, also can in above-mentioned composition, add glyoxaline compound (glyoxal ethyline, 1,2 dimethylimidazole, 2-methyl-4-methylimidazole, 2-ethyl-4-ethyl imidazol(e), 2-phenylimidazole), tensio-active agent additives such as (fluorine class tensio-active agents etc.).
So just can make the homodisperse shaping of CB powder semi-conductivity aromatic amides acid composition.
B-2. semi-conductivity endless tubular polyimide film
Next, the manufacturing process to the semi-conductivity endless tubular polyimide film that uses above-mentioned synthetic semi-conductivity aromatic amides acid composition is illustrated.
This manufacturing process adopts the method for rotary forming that uses rotor.At first semi-conductivity aromatic amides acid composition is injected the inner face of rotor, evenly curtain coating is all in inner face.
The method of injection-curtain coating is, for example, and in the rotor that stops, inject to obtain final film thickness after the semi-conductivity aromatic amides acid composition of suitable amount, slowly improve speed of rotation, up to the speed that centrifugal force works, all in inner face by the even curtain coating of centrifugal force.Perhaps, injection-curtain coating does not use centrifugal force passable yet.For example, the slot-shaped nozzle in that the inner face configuration of cylinder is grown crosswise continues this cylinder of rotation lentamente, and this nozzle (with than this speed of rotation faster speed) also rotates.Then, the semi-conductivity aromatic amides acid composition with shaping usefulness all sprays to this cylinder inner face equably from this nozzle.
No matter which kind of method is made minute surface with the inner face of rotor, prevents the barrier of fluid seepage along the circumference setting in edges at two ends.This cylinder mounting is on the rotation roller, and the rotation by this roller can be rotated indirectly.
Heating is for example to dispose thermal source such as far infra-red heater around this cylinder, carry out indirect heating from the outside.The size of this cylinder depends on the size of desirable semiconduction tubulose PI film.
Heating slowly heats up the cylinder inner face, at first is about 100～190 ℃, preferably reaches (the 1st heating phase) about 110～130 ℃.Heat-up rate for example gets final product about 1～2 ℃/min.Kept under said temperature 1～2 hour, and made only about half of above solvent evaporates, being shaped has self-supportive tubular film.In order to carry out imidization, need reach the temperature more than 280 ℃, but if heat with high like this temperature just beginning most, then not only polyimide shows high crystallization, influence the dispersion state of CB, and existence can't form tough problems such as overlay film.Therefore, as the 1st heating phase, ceiling temperature is the highest to be controlled at about 190 ℃, stops polycondensation under this temperature, just obtains tough tubulose PI film.
If next this stage, as the 2nd heating phase, heats in order to finish imidization after finishing, its temperature is (preferred about 300～380 ℃) about 280～400 ℃.At this moment neither reach this temperature suddenly from the temperature of the 1st heating phase, to reach this temperature better but slowly heat up.
In addition, the 2nd heating phase, can be directly under being attached to the state of rotor inner face, the endless tubular film carries out, also can after the 1st heating phase finished, the endless tubular film be peeled off taking-up from rotor, other heater means that is used to reach imidization is provided, is heated to 280～400 ℃.The used time of this imidization, be about usually about 2～3 hours.Therefore, the used time of the 1st and the 2nd whole operations of heating phase, be generally about 4～7 hours.
So just made semi-conductivity endless tubular PI film of the present invention.Though there is no particular limitation for the thickness of this film, be generally about 50～150 μ m, be preferably about 60～120 μ m.During especially for the intermediate duplication band of electrofax mode, be preferably about 75～100 μ m.
The semi-conductivity of this film is that (resistance characteristic of (hereinafter referred to as " SR ") the two common decision of Ω/), this characteristic is to give by the blending dispersion of CB powder by volume specific resistance (Ω cm) (hereinafter referred to as " VR ") and surface resistivity.And the scope of this resistivity, can freely change by the combined amount of CB powder basically.As the electrical resistivity range of film of the present invention, can illustratively be VR:10 2～10 14, SR:10 3～10 15,, can illustratively be VR:10 as preferable range 6～10 13, SR:10 7～10 14These electrical resistivity range can reach at an easy rate by the use level that adopts above-mentioned CB powder.In addition, the CB content in the film of the present invention is generally about 3～25 weight %, about preferred 10～20 weight %.
Semi-conductivity PI film of the present invention has the very resistivity of homogeneous.That is, the unique point of semi-conductivity PI film of the present invention is, the variability of the logarithm conversion value of surface resistivity SR and volume specific resistance VR is little, and in film in the full measuring point, the standard deviation of logarithm conversion value separately is in 0.2, in preferred 0.15.In addition, have the little such feature of difference of the surface resistivity (logarithm conversion value) at the film surface and the back side, this difference is in 0.4, preferably in 0.2.And possess following feature: the logarithm conversion value LogSR of surface resistivity deducts the value of the logarithm conversion value LogVR of volume specific resistance, can maintain 1.0～3.0, preferred 1.3～3.0 such high values.
Why PI film of the present invention has the electrical characteristic of above-mentioned excellence, thinks because in the manufacturing process of this film, has adopted " aromatic amides acid oligomer " and CB powder blended semi-conductivity aromatic amides acid composition mutually.That is, think in said composition that the CB powder is dispersed in the aromatic amides acid oligomer, owing to can in film manufacturing process, keep this uniformly dispersed and polymer quantification, so just can give the characteristic of PI film excellence of the present invention.
PI film of the present invention is because its excellent function such as resistance characteristic serves many purposes.For example, as the important use that needs charged characteristic, can enumerate the intermediate duplication band of the electrofax mode that is used for color printer, color copy machine etc. etc.As this band, necessary semi-conductivity (resistivity) for example is VR10 9～10 12, SR10 10～10 13, can use semi-conductivity endless tubular PI film of the present invention with being well suited for.
Non-conductive or semi-conductivity PI film of the present invention, the excellent performance as band has high yield strength (σ Y) and breaking tenacity (σ Cr).Yield strength (σ Y) more than 120MPa, 120～160MPa particularly, the ratio (σ of breaking tenacity and yield strength Cr/ σ Y) more than 1.10, particularly about 1.10～1.35.
C. the 3rd invention
Semi-conductivity endless tubular polyimide class film of the present invention (below be also referred to as " semi-conductivity tubulose PI class film ") is to use semiconductive polyimide class precursor composition (below be also referred to as " semi-conductivity PI precursor composition ") to make by spinning-shaping and heat treated (imidization).
C-1. semiconductive polyimide class precursor composition
Semiconductive polyimide class precursor composition of the present invention, be aromatic tetracarboxylic acid's diester more than 2 kinds and aromatic diamine to be dissolved in the nylon salt type monomer solution that forms in the organic polar solvent with equimolar amount roughly, mix high-molecular weight polyimide precursor solution or high-molecular weight polyamidoimide solution, the modulation mixing solutions is dispersed in this mixing solutions carbon black (below be also referred to as " CB ") and makes.
(1) aromatic tetracarboxylic acid's diester (half ester)
As the aromatic tetracarboxylic acid's diester more than 2 kinds of shaping raw material, use the mixture of at least a asymmetry aromatic tetracarboxylic acid's diester and at least a symmetry aromatic tetracarboxylic acid's diester.
Below, be illustrated with regard to asymmetry aromatic tetracarboxylic acid's diester used in the present invention.
Here, so-called asymmetry aromatic tetracarboxylic acid, can enumerate at monocycle or polycyclic aromatic nucleus (phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, anthracene nucleus) go up, 4 carboxyls are bonded to the compound on the non-point symmetry position, perhaps 2 monocycle aromatic nucleus (phenyl ring etc.) with-CO-,-CH 2-,-SO 2-wait on the crosslinked compound of base or singly-bound, 4 carboxyls are bonded to the compound on the non-point symmetry position.
As asymmetry aromatic tetracarboxylic acid's object lesson, can enumerate 1,2,3,4-benzene tertacarbonic acid, 1,2,6,7-naphthalene tetracarboxylic acid, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4 '-benzophenone tetracarboxylic acid, 2,3,3 ', 4 '-phenyl ether tetracarboxylic acid, 2,3,3 ', 4 '-ditan tetracarboxylic acid, 2,3,3 ', 4 '-diphenylsulfone acid etc.
As asymmetry aromatic tetracarboxylic acid's diester used in the present invention (half ester), can enumerate above-mentioned asymmetry aromatic tetracarboxylic acid's diester, specifically, can enumerate an esterified compound that among 4 carboxylic acids of above-mentioned asymmetry tetracarboxylic acid, has in 2 adjacent on the esterified and aromatic nucleus of 2 carboxyls carboxyls.
As 2 esters in above-mentioned asymmetry aromatic tetracarboxylic acid's diester, can enumerate two lower alkyl esters, two C such as preferred dimethyl ester, diethyl ester, dipropyl 1-3Alkyl ester (particularly dimethyl ester).
Among above-mentioned asymmetry aromatic carboxylic acid diester, preferably use 2,3,3 ', 4 '-biphenyltetracarboxyacid acid dimethyl ester, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid diethyl ester especially preferably uses 2,3,3 ', 4 '-biphenyltetracarboxyacid acid dimethyl ester.
In addition, above-mentioned asymmetry aromatic tetracarboxylic acid's diester can adopt commercially available or with the known method manufacturing.For example, by making the corresponding alcohol of 1 part of corresponding asymmetry aromatic tetracarboxylic acid's dianhydride and 2 parts (mol ratio) (lower alcohol, preferred C 1-3Alcohol etc.) known method such as reaction can be made at an easy rate.By such method, open loop just can be manufactured on the diester (half ester) that has ester group and carboxyl on the adjacent carbon of aromatic nucleus respectively with the alcohol reaction as the acid anhydrides of raw material.
Then, symmetry aromatic tetracarboxylic acid's diester used in the present invention below is described.
Here, so-called symmetry aromatic tetracarboxylic acid, can enumerate at monocycle or polycyclic aromatic nucleus (phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, anthracene nucleus) go up, 4 carboxyls are bonded to the compound on the point symmetry position, perhaps 2 monocycle aromatic nucleus (phenyl ring etc.) with-CO-,-O-,-CH 2-,-SO 2-wait on the crosslinked compound of base or singly-bound, 4 carboxyls are bonded to the compound on the point symmetry position.
As symmetry aromatic tetracarboxylic acid's object lesson, can enumerate 1,2,4,5-benzene tertacarbonic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-phenyl ether tetracarboxylic acid, 3,3 ', 4,4 '-ditan tetracarboxylic acid, 3,3 ', 4,4 '-diphenylsulfone acid etc.
As symmetry tetracarboxylic acid diester used in the present invention (half ester), can enumerate above-mentioned symmetry aromatic tetracarboxylic acid's diester (half ester), specifically, can enumerate an esterified compound that among 4 carboxyls of above-mentioned symmetry tetracarboxylic acid, has in 2 adjacent on the esterified and aromatic nucleus of 2 carboxyls carboxyls.
As 2 esters in above-mentioned symmetry aromatic tetracarboxylic acid's diester, can enumerate two lower alkyl esters, C such as preferred dimethyl ester, diethyl ester, dipropyl 1-3Alkyl ester (particularly dimethyl ester).
Among above-mentioned symmetry aromatic carboxylic acid diester, preferably use 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dimethyl ester, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid diethyl ester, 1,2,4,5-benzene tertacarbonic acid dimethyl ester, 1,2,4,5-benzene tertacarbonic acid diethyl ester especially preferably uses 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dimethyl ester.
In addition, above-mentioned symmetry aromatic tetracarboxylic acid's diester can adopt commercially available or with the known method manufacturing.For example, by making the corresponding alcohol of 1 part of corresponding symmetry aromatic tetracarboxylic acid's dianhydride and 2 parts (mol ratio) (lower alcohol, preferred C 1-3Alcohol etc.) known method such as reaction can be made at an easy rate.By such method, open loop just can be manufactured on the diester (half ester) that has ester group and carboxyl on the adjacent carbon of aromatic nucleus respectively with the alcohol reaction as the acid anhydrides of raw material.
The ratio of mixture of asymmetry and symmetric aromatic tetracarboxylic acid's diester, special stipulation is, asymmetry aromatic tetracarboxylic acid's diester is about 10～50 moles of % (preferred 20～40 moles of %), and symmetry aromatic tetracarboxylic acid's diester is about 90～50 moles of % (preferred 80～60 moles of %).Particularly asymmetry aromatic tetracarboxylic acid diester is about 20～30 moles of %, and symmetry aromatic tetracarboxylic acid's diester is to use about 70～80 moles of % to be well suited for.
Why must cooperate above-mentioned asymmetry and symmetric aromatic tetracarboxylic acid's composition, the reasons are as follows.When only utilizing symmetry aromatic tetracarboxylic acid diester, because polyimide film shows crystallinity, so overlay film efflorescence and can't carry out membranization in heat treated.On the other hand, when only utilizing asymmetry aromatic tetracarboxylic acid diester, though can be configured as endless tubular PI film, but a little less than the yield strength and spring rate of this film that is obtained, when using as rotating band, bad response in driving not only, and the stage rotates problems such as band elongation in the early stage.
Relative therewith, if use mixed aromatic tetracarboxylic acid diester, then can obtain high system film (plasticity), and can obtain to have the semi-conductivity endless tubular PI film of high-yield strength and snappiness rate.
In addition, the applicant thinks, by adding asymmetry aromatic tetracarboxylic acid diester, can make the bending of polyamic acid molecule, produces snappiness.
Therefore, the coexistence effect of aromatic tetracarboxylic acid's derivative of above-mentioned symmetry and asymmetry can access performance most effectively when the two ratio of mixture as noted above.
(2) aromatic diamine
As aromatic diamine, can enumerate the compound that on an aromatic nucleus (phenyl ring etc.), has 2 amino, perhaps the aromatic nucleus more than 2 (phenyl ring etc.) with-O-,-S-,-CO-,-CH 2-,-SO-,-SO 2-wait base or the crosslinked compound of singly-bound with 2 amino.Specifically, for example, p-penylene diamines, o-penylene diamines, m-penylene diamines, 4,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino, two phenylcarbamoyls, 4,4 '-diaminodiphenylmethane, 1, two (4-amino-benzene oxygen) benzene of 4-etc.Wherein, preferred especially 4,4 '-diaminodiphenyl oxide.This is because by using these aromatic diamines, when reaction is more successfully carried out, can make more tough and the film of high heat resistance more.
(3) nylon salt type monomer solution
Above-mentioned more than 2 kinds aromatic tetracarboxylic acid's diester and aromatic diamine with equimolar amount uniform dissolution roughly in organic polar solvent, modulation nylon salt type monomer solution.Two composition uniform dissolution in organic polar solvent the time, also can heated (for example, about 40～70 ℃) as required.Known blending meanss such as use stirring are dissolved in the organic polar solvent two compositions and get final product.
As employed organic polar solvent, preferably proton there is inertia class organic polar solvent, for example, use N-N-methyl-2-2-pyrrolidone N-(hereinafter referred to as " NMP "), N, dinethylformamide, N, N-diethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, 1,3-dimethyl-2-imidazolone etc.The mixing solutions of wherein one or more all can.Preferred especially NMP.The usage quantity of organic polar solvent with respect to measuring 100 weight parts as the aromatic tetracarboxylic acid's diester more than 2 kinds of raw material and the total of aromatic diamine, is decided to be that (about preferred 120～200 weight parts) get final product about 100～300 weight parts.
The applicant thinks, above-mentioned nylon salt type monomer solution, and for example, in organic polar solvent, the ion pair of the carboxylic acid ion of aromatic tetracarboxylic acid's diester and the ammonium ion of aromatic diamine remains free state (for example with reference to following formula) in fact.In addition, because come down to free state,, has the advantage that to do one's utmost to reduce employed quantity of solvent so be easy to be dissolved in the above-mentioned organic polar solvent.
Figure A20048004293200361
(in the formula, Ar represents to remove 4 valency bases behind 2 carboxyls and 2 ester groups from the aromatic tetracarboxylic acid, and 2 divalent bases behind the amino are removed in Ar ' expression from aromatic diamine, and R represents alkyl.)
(4) high molecular polyimide precursor solution or superpolyamide imide solution
As high molecular polyimide precursor solution, the use number-average molecular weight is the polyamic acid solution more than 10000; As the superpolyamide imide solution, the use number-average molecular weight is the polyamidoimide solution more than 10000.In addition, the number-average molecular weight in this specification sheets is the value of being measured with GPC method (solvent: NMP, polyethylene oxide convert).
Polyamic acid solution
Number-average molecular weight for example, can use biphenyl tetracarboxylic dianhydride and diaminodiphenyl oxide composition as starting raw material, by the known method manufacturing in organic polar solvent at the polyamic acid solution more than 10000.Organic polar solvent can use employed organic polar solvent in above-mentioned nylon salt type monomer solution.
As biphenyl tetracarboxylic dianhydride, for example can enumerate 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride (a-BPDA), 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (s-BPDA), 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride etc.
As the diaminodiphenyl oxide composition, for example, can enumerate 4,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide etc.
The use level of biphenyl tetracarboxylic dianhydride and diaminodiphenyl oxide composition gets final product for equimolar amount roughly.The polycondensation of the two can be adopted known method, for example, adducible method is, at room temperature (about 15～30 ℃) add the biphenyltetracarboxyacid acid composition in the solution that contains the diaminodiphenyl oxide composition, make it that amidation take place, the modulation polyamic acid solution.The number-average molecular weight of the polyamic acid that is obtained is preferably 12000～20000 more than 10000.
Polyamidoimide solution
Number-average molecular weight is at the polyamidoimide solution more than 10000, for example, and in organic polar solvent, by making by known reactions such as acid anhydrides that trimellitic acid 1,2-anhydride and benzophenone tetracarboxylic anhydride constituted and aromatic isocyanate polycondensations.Organic polar solvent can use the employed organic polar solvent of above-mentioned nylon salt type monomer solution.
In the acid anhydrides, trimellitic acid 1,2-anhydride is about 70～95 moles of %, and the benzophenone tetracarboxylic anhydride is to get final product about 5～30 moles of %.
As aromatic isocyanate, for example, can enumerate ditolylene vulcabond, 3,3 '-sulfobenzide vulcabond, isophorone diisocyanate, 1,4-vulcabond, 4,4 '-dicyclohexyl methane diisocyanate, m-Xylene Diisocyanate, p-Xylene Diisocyanate, 1,4-cyclohexalene vulcabond etc.
The carboxyl in the acid composition and the sum of anhydride group are measured better about equally with the sum use of aromatic isocyanate base.
The number-average molecular weight of polyamidoimide is preferably about 15000～20000 more than 10000.
(5) mixing solutions
By with above-mentioned nylon salt type monomer solution and high molecular polyimide precursor solution or the mixing of superpolyamide imide solution, modulate mixing solutions.This mixing can be adopted known method such as spiral mixer, magnetic stirrer, ball mill.
The combined amount of the two (ratio) is, with respect to non-volatile content weight 100 weight parts in the nylon salt type monomer solution, the non-volatile content weight of high molecular polyimide precursor solution (particularly number-average molecular weight is at the polyamic acid solution more than 10000) or superpolyamide imide solution (number-average molecular weight is at the polyamidoimide solution more than 10000) is preferably in the scope of (about preferred 20～30 weight parts) about 10～50 weight parts.In addition, the what is called of using in this manual " non-volatile content weight " is meant the amount of the method mensuration of being put down in writing with Embodiment C-1.
In addition, the non-volatile content weight of high molecular polyimide precursor solution or superpolyamide imide solution, with respect to the monomeric non-volatile content weight of nylon salt type, if less than 10 weight parts then are difficult to reach effect of the present invention, in addition, if add carbon black in surpassing the solution of 50 weight parts, then the increment rate of viscosity will significantly raise, and sooty is pulverized the difficulty that becomes, the result just needs the organic polar solvents that add more, makes production efficiency reduce.
(6) semi-conductivity PI precursor composition
Next, the CB powder is dispersed in this mixing solutions modulation semi-conductivity PI precursor composition.
Use the reason of CB powder to be in order to give resistance characteristic, (with other metal and metal conductive oxide material compared known to usually), and blending dispersion between the monomer mixture solution that modulates and stability (after the blending dispersion through time change) excellence, and polycondensation there is not detrimentally affect.
This CB powder differently has a multiple physical property (resistance, volatile matter, specific surface area, particle diameter, pH value, DBP oil number etc.) according to what it made raw material (Sweet natural gas, acetylene gas, tar etc.) and create conditions (combustion conditions).Even the CB powder of selecting a small amount of as far as possible blending dispersion, desirable resistance also can not produce deviation, stablize and obtain easily is better.
This electroconductibility CB powder, usually median size is about 15～65nm, when the intermediate duplication band that is used in particular for employed electrofax mode such as color printer, color copy machine etc., preferred median size is about 20～40nm.
The carbon black of conductive finger absolute altitudes such as section's qin carbon black (ketjen black) and Shawinigan black, 2 cohesions take place easily, and (structure structure), causes the chain of electroconductibility easily, is difficult to be controlled at semiconductor regions.So it is effective using the acidic carbon black that is difficult to recurring structure formation.
For example, can enumerate furnace black that thermally oxidized black, oxide treatment cross etc.Specifically, but the Special Black 4 of illustration Degusa corporate system (pH3, volatile matter 14%, particle diameter 25nm), Special Black 5 (pH3, volatile matter 15%, particle diameter 20nm).
The blending means of CB powder if CB powder uniform mixing is scattered in the mixed solution C, then is not particularly limited.For example, use ball mill, simpson mill, ultrasonic wave shredder etc.
The amount of the CB powder that is added, measure 100 weight parts as aromatic tetracarboxylic acid's composition of nylon salt type raw material monomer and organic diamine and (2) as the acid anhydrides of high molecular polyimide precursor raw material and diamines or as the acid anhydrides of superpolyamide imide raw material and the total of aromatic isocyanate with respect to (1), preferably cooperate (about preferred 10～30 weight parts) about 5～40 weight parts.Here, why using the CB powder in above-mentioned scope, is volume specific resistance (VR) and the surface resistivity (SR) that is in semiconductor regions in order to give to film.Under be limited to 5 the amount part about more than be because, in order to obtain competent electroconductibility, the amount of this degree is necessary; On be limited to about 40 weight parts be because, when showing lower resistance, keep plasticity, prevent the reduction of film self physical property.
The concentration of the non-volatile content in the semi-conductivity PI precursor composition is about 20～60 weight %, and the concentration of CB powder is (about preferred 9～23 weight %) about 5～30 weight % in this non-volatile content.In addition, what is called as used in this specification " non-volatile content concentration " is meant the concentration of the method mensuration of being put down in writing with Embodiment C-1.
In addition, in the scope that effect of the present invention is had no adverse effects, also can in above-mentioned composition, add glyoxaline compound (glyoxal ethyline, 1,2 dimethylimidazole, 2-methyl-4-methylimidazole, 2-ethyl-4-ethyl imidazol(e), 2-phenylimidazole), tensio-active agent additives such as (fluorine class tensio-active agents etc.).
Make like this and make the homodisperse shaping of CB powder semi-conductivity PI precursor composition.
In semi-conductivity PI precursor composition of the present invention, by high molecular polyimide precursor solution or superpolyamide imide solution are mixed in the nylon salt type monomer, the carbon black homodisperse the storage stability of state significantly improve.And, the semi-conductivity PI precursor composition that has used it is rotated the conductive tubular polyimide film that shaping obtains, be endowed the electroconductibility that has the resistivity of very stable and homogeneous at its thickness direction.Though its reason is also uncertain, its reason of applicant is: have the polymkeric substance with higher number average molecular weight in the polyimide precursor composition, this component of polymer and carbon black have suppressed the sooty cohesion by physical connection or viscosity.The applicant thinks in addition, has not only relaxed the influence of the suffered centrifugal force of the carbon black pellet that is in the spinning-shaping because of the viscosity of polymkeric substance, and the temperature convection can relax solvent evaporates time the and the influence of evaporation convection current.And, also have the effect of slowing down the polyimide speed of response that causes because of heating.
II. electroconductibility endless tubular polyimide class film
Next, the manufacturing process to the conductive tubular PI class film that uses above-mentioned synthetic semi-conductivity PI precursor composition is illustrated.
This manufacturing process adopts the method for rotary forming that uses rotor.At first semi-conductivity PI precursor composition is injected the inner face of rotor, evenly curtain coating is all in inner face.
The method of injection-curtain coating is, for example, and in the rotor that stops, inject to obtain final film thickness after the semi-conductivity PI precursor composition of suitable amount, slowly improve speed of rotation, up to the speed that centrifugal force works, all in inner face by the even curtain coating of centrifugal force.Perhaps, injection-curtain coating does not use centrifugal force passable yet.For example, the slot-shaped nozzle in that the inner face configuration of rotor is grown crosswise continues this cylinder of rotation lentamente, and this nozzle (with than this speed of rotation faster speed) also rotates.Then, the semi-conductivity PI precursor composition with shaping usefulness all sprays to this cylinder inner face equably from this nozzle.
No matter which kind of method is made minute surface with the inner face of rotor, prevents the barrier of fluid seepage along the circumference setting in edges at two ends.This cylinder mounting is on the rotation roller, and the rotation by this roller can be rotated indirectly.
Heating is for example to dispose thermal source such as far infra-red heater around this cylinder, carry out indirect heating from the outside.The size of this cylinder depends on the size of desirable semiconduction tubulose PI film.
Heating slowly heats up the cylinder inner face, at first is about 100～190 ℃, preferably reaches (the 1st heating phase) about 110～130 ℃.Heat-up rate for example gets final product about 1～2 ℃/min.Kept under said temperature 1～3 hour, and made only about half of above solvent evaporates, being shaped has self-supportive tubular film.In order to carry out imidization, need reach the temperature more than 280 ℃, but if heat with high like this temperature just beginning most, then not only polyimide shows high crystallization, influence the dispersion state of CB, and existence can't form tough problems such as overlay film.Therefore, as the 1st heating phase, ceiling temperature is the highest to be controlled at about 190 ℃, stops polycondensation under this temperature, just obtains tough tubulose PI film.
If next this stage, as the 2nd heating phase, heats in order to finish imidization after finishing, its temperature is (preferred about 300～380 ℃) about 280～400 ℃.At this moment neither reach this temperature suddenly from the temperature of the 1st heating phase, to reach this temperature better but slowly heat up.
In addition, the 2nd heating phase, can be directly under being attached to the state of rotor inner face, the endless tubular film carries out, also can after the 1st heating phase finished, the endless tubular film be peeled off taking-up from rotor, other heater means that is used to reach imidization is provided, is heated to 280～400 ℃.The used time of this imidization, be about usually about 2～3 hours.Therefore, the used time of the 1st and the 2nd whole operations of heating phase, be generally about 4～7 hours.
So just made electroconductibility endless tubular polyimide class film of the present invention.Though there is no particular limitation for the thickness of this film, be generally about 30～200 μ m, be preferably about 50～120 μ m.During especially for the intermediate duplication band of electrofax mode, be preferably about 70～100 μ m.
The semi-conductivity of this film is that (resistance characteristic of (hereinafter referred to as " SR ") the two common decision of Ω/), this characteristic is to give by the blending dispersion of CB powder by volume specific resistance (Ω cm) (hereinafter referred to as " VR ") and surface resistivity.And the scope of this resistivity, can freely change by the combined amount of CB powder basically.As the electrical resistivity range of film of the present invention, can illustratively be VR:10 2～10 14, SR:10 3～10 15,, can illustratively be VR:10 as preferable range 6～10 13, SR:10 7～10 14These electrical resistivity range can reach at an easy rate by the use level that adopts above-mentioned CB powder.In addition, the CB content in the film of the present invention is generally about 5～30 weight %, about preferred 9～23 weight %.
Semi-conductivity PI film of the present invention has the very resistivity of homogeneous.That is, the unique point of semi-conductivity PI film of the present invention is, the variability of the logarithm conversion value of surface resistivity SR and volume specific resistance VR is little, and in film in the full measuring point, the standard deviation of logarithm conversion value separately is in 0.2, in preferred 0.15.In addition, have the little such feature of difference of the surface resistivity (logarithm conversion value) at the film surface and the back side, this difference is in 0.4, preferably in 0.2.And possess following feature: the logarithm conversion value LogSR of surface resistivity deducts the value of the logarithm conversion value LogVR of volume specific resistance, can maintain 1.0～3.0, preferred 1.5～3.0 such high values.
Why PI film of the present invention has the electrical characteristic of above-mentioned excellence, think, because by mixing high molecular polyimide precursor or superpolyamide imide precursor solution, CB is incorporated in the mutual entanglement structure of this macromolecular chain equably by physical property ground, so be difficult to be subjected to the influence of solvent evaporation in the film manufacturing process and the monomeric polymer quantification of nylon salt type etc., can be with the CB dispersion state of the homogeneous that in precursor composition solution, reaches and obtain electroconductibility endless tubular polyimide class film.
PI film of the present invention is because its excellent function such as resistance characteristic serves many purposes.For example, as the important use that needs charged characteristic, can enumerate the intermediate duplication band of the electrofax mode that is used for color printer, color copy machine etc. etc.As this band, necessary semi-conductivity (resistivity) for example is VR10 9～10 12, SR10 10～10 13, can use semi-conductivity endless tubular PI class film of the present invention with being well suited for.
Semi-conductivity PI film of the present invention, the excellent performance as band has high yield strength (σ Y) and breaking tenacity (σ Cr).Yield strength (σ Y) more than 120MPa, 120～160MPa particularly, the ratio (σ of breaking tenacity and yield strength Cr/ σ Y) more than 1.10, particularly about 1.10～1.35.
D. the 4th invention
Semi-conductivity endless tubular polyimide film of the present invention (below be also referred to as " semi-conductivity tubulose PI film ") is to use semi-conductivity high density polyimide precursor composition (below be also referred to as " semi-conductivity high density PI precursor composition ") to make by spinning-shaping and heat treated (imidization).
D-1. semi-conductivity high density polyimide precursor composition
Semi-conductivity high density polyimide precursor composition of the present invention, be that carbon black (below be also referred to as " CB ") is dispersed in the carbon black dispersion liquid that forms in the organic polar solvent, dissolved aromatic tetracarboxylic acid's diester and aromatic diamine manufacturing with equimolar amount roughly.That is, it has following feature: make as the such order of monomer (aromatic tetracarboxylic acid's diester and aromatic diamine are equimolar amount) of shaping raw material by adding equimolar amount in the homodisperse liquid that is increased in prior synthetic CB.
(1) carbon black dispersion liquid
In the present invention, in order to give semi-conductivity, in the PI precursor composition, use electroconductibility CB powder.Use the reason of this CB powder to be, the blending dispersion of CB in (with other metal or metal conductive oxide material compared known to usually) synthetic semi-conductivity high density polyimide precursor composition of institute and dispersion stabilization (after the blending dispersion through time variation) excellence, and polycondensation do not had detrimentally affect.
This CB powder differently has a multiple physical property (resistance, volatile matter, specific surface area, particle diameter, pH value, DBP oil number etc.) according to what it made raw material (Sweet natural gas, acetylene gas, tar etc.) and create conditions (combustion conditions).Even the CB powder of selecting a small amount of as far as possible blending dispersion, desirable resistance also can not produce deviation, stablize and obtain easily is better.
This electroconductibility CB powder, median size is about 15～65nm usually, when being used in particular for the intermediate duplication band of employed electrofax modes such as color printer, color copy machine, preferred median size is about 20～40nm.
2 cohesions (structure structure) take place in the carbon black of conductive finger absolute altitudes such as section's qin carbon black and Shawinigan black easily, cause the chain of electroconductibility easily, are difficult to be controlled at semiconductor regions.So it is effective using the acidic carbon black that is difficult to recurring structure formation.
For example, can enumerate furnace black that thermally oxidized black, oxide treatment cross etc.Specifically, but the Special Black 4 of illustration Degusa corporate system (pH3, volatile matter 14%, particle diameter 25nm), Special Black 5 (pH3, volatile matter 15%, particle diameter 20nm).
As the employed organic polar solvent of carbon black dispersion liquid, preferably proton there is inertia class organic polar solvent, for example, use N-N-methyl-2-2-pyrrolidone N-(hereinafter referred to as " NMP "), N, dinethylformamide, N, N-diethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, 1,3-dimethyl-2-imidazolone etc.Can use one or more mixing solutions wherein.Preferred especially NMP.
Carbon black dispersion liquid is that the CB powder is dispersed in manufacturing in the above-mentioned organic polar solvent.The blending means of CB powder if CB powder uniform mixing is scattered in method in the organic polar solvent, then is not particularly limited.For example, use ball mill, simpson mill, ultrasonic wave shredder etc.
The use level of CB powder with respect to organic polar solvent 100 weight parts, is about 3～25 weight parts, about preferred 5～15 weight parts.The scope of this use level is to make the viscosity increase of organic polar solvent or the scope that CB can not form 2 aggregates by Van der Waals force.In addition, why with respect to organic polar solvent 100 weight parts, being limited to more than 3 weight parts down, is the non-volatile content concentration for the semi-conductivity high density polyimide precursor composition that does not reduce manufacturing, and this is necessary amount.Being limited to below 25 weight parts why, is in order to make the distance between homodisperse CB particle and the CB particle sufficient, to prevent 2 cohesions that cause because of Van der Waals force.
(2) aromatic tetracarboxylic acid's diester (half ester)
As the aromatic tetracarboxylic acid's diester more than 2 kinds of shaping raw material, use the mixture of at least a asymmetry aromatic tetracarboxylic acid's diester and at least a symmetry aromatic tetracarboxylic acid's diester.
Below be illustrated with regard to asymmetry aromatic tetracarboxylic acid's diester used in the present invention.
Here, so-called asymmetry aromatic tetracarboxylic acid, can enumerate at the compound that monocycle or polycyclic aromatic nucleus (phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, anthracene nucleus etc.) are gone up, 4 carboxyls are bonded to non-point symmetry position, perhaps 2 monocycle aromatic nucleus (phenyl ring etc.) with-CO-,-CH 2-,-SO 2-wait on the crosslinked compound of base or singly-bound, compound that 4 carboxyls are bonded to non-point symmetry position.
As asymmetry aromatic tetracarboxylic acid's object lesson, can enumerate 1,2,3,4-benzene tertacarbonic acid, 1,2,6,7-naphthalene tetracarboxylic acid, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4 '-benzophenone tetracarboxylic acid, 2,3,3 ', 4 '-phenyl ether tetracarboxylic acid, 2,3,3 ', 4 '-ditan tetracarboxylic acid, 2,3,3 ', 4 '-diphenylsulfone acid etc.
As asymmetry aromatic tetracarboxylic acid's diester used in the present invention (half ester), can enumerate above-mentioned asymmetry aromatic tetracarboxylic acid's diester, specifically, can enumerate an esterified compound that in 4 carboxylic acids of above-mentioned asymmetry aromatic tetracarboxylic acid, has in 2 adjacent on the esterified and aromatic nucleus of 2 carboxyls carboxyls.
As 2 esters in above-mentioned asymmetry aromatic tetracarboxylic acid's diester, can enumerate two lower alkyl esters, C such as preferred dimethyl ester, diethyl ester, dipropyl 1-3Alkyl ester (particularly dimethyl ester).
Among the diester of above-mentioned asymmetry aromatic carboxylic acid, preferably use 2,3,3 ', 4 '-biphenyltetracarboxyacid acid dimethyl ester, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid diethyl ester especially preferably uses 2,3,3 ', 4 '-biphenyltetracarboxyacid acid dimethyl ester.
In addition, above-mentioned asymmetry aromatic tetracarboxylic acid's diester can adopt commercially available or with the known method manufacturing.For example, by making the corresponding alcohol of 1 part of corresponding asymmetry aromatic tetracarboxylic acid's dianhydride and 2 parts (mol ratio) (lower alcohol, preferred C 1-3Alcohol etc.) reaction can be made at an easy rate.By such method, open loop just can be manufactured on the diester (half ester) that has ester group and carboxyl on the carbon adjacent on the aromatic nucleus respectively with the alcohol reaction as the acid anhydrides of raw material.
Next, symmetry aromatic tetracarboxylic acid's used in the present invention diester below is described.
Here, so-called symmetry aromatic tetracarboxylic acid, can enumerate at the compound that monocycle or polycyclic aromatic nucleus (phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, anthracene nucleus etc.) are gone up, 4 carboxyls are bonded to point symmetry position, perhaps 2 monocycle aromatic nucleus (phenyl ring etc.) with-CO-,-O-,-CH 2-,-SO 2-wait on the crosslinked compound of base or singly-bound, compound that 4 carboxyls are bonded to point symmetry position.
As symmetry aromatic tetracarboxylic acid's object lesson, can enumerate 1,2,4,5-benzene tertacarbonic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-phenyl ether tetracarboxylic acid, 3,3 ', 4,4 '-ditan tetracarboxylic acid, 3,3 ', 4,4 '-diphenylsulfone acid etc.
As symmetry aromatic tetracarboxylic acid's diester used in the present invention (half ester), can enumerate above-mentioned symmetry aromatic tetracarboxylic acid's diester (half ester), specifically, can enumerate an esterified compound that among 4 carboxylic acids of above-mentioned symmetry aromatic tetracarboxylic acid, has in 2 adjacent on the esterified and aromatic nucleus of 2 carboxyls carboxyls.
As 2 esters in above-mentioned symmetry aromatic tetracarboxylic acid's diester, can enumerate two lower alkyl esters, C such as preferred dimethyl ester, diethyl ester, dipropyl 1-3Alkyl ester (particularly dimethyl ester).
Among above-mentioned symmetry aromatic carboxylic acid diester, preferably use 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dimethyl ester, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid diethyl ester, 1,2,4,5-benzene tertacarbonic acid dimethyl ester, 1,2,4,5-benzene tertacarbonic acid diethyl ester especially preferably uses 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dimethyl ester.
In addition, above-mentioned symmetry aromatic tetracarboxylic acid's diester can adopt commercially available or with the known method manufacturing.For example, by making the corresponding alcohol of 1 part of corresponding symmetry aromatic tetracarboxylic acid's dianhydride and 2 parts (mol ratio) (lower alcohol, preferred C 1-3Alcohol etc.) known method such as reaction can be made at an easy rate.By such method, open loop just can be manufactured on the diester (half ester) that has ester group and carboxyl on the carbon adjacent on the aromatic nucleus respectively with the alcohol reaction as the acid anhydrides of raw material.
The ratio of mixture of asymmetry and symmetry aromatic tetracarboxylic acid diester, special stipulation is, asymmetry aromatic tetracarboxylic acid's diester is about 10～50 moles of % (preferred 20～40 moles of %), and symmetry aromatic tetracarboxylic acid's diester is about 90～50 moles of % (preferred 80～60 moles of %).Particularly, asymmetry aromatic tetracarboxylic acid's diester is about 20～30 moles of %, and symmetry aromatic tetracarboxylic acid's diester is to use about 70～80 moles of % to be well suited for.
Why must cooperate above-mentioned symmetry and asymmetry aromatic tetracarboxylic acid diester, the reasons are as follows.When only utilizing symmetry aromatic tetracarboxylic acid diester, because polyimide film shows crystallinity, so overlay film efflorescence and can't carry out membranization in heat treated.On the other hand, when only utilizing asymmetry aromatic tetracarboxylic acid derivative, though can be configured as endless tubular PI film, but a little less than the yield strength and spring rate of this film that is obtained, when using as rotating band, bad response in driving not only, and the stage rotates problems such as band elongation in the early stage.
Relative therewith, if use mixed aromatic tetracarboxylic acid diester, then can obtain high system film (plasticity), and can obtain to have the semi-conductivity endless tubular PI film of high-yield strength and snappiness rate.
In addition, the applicant thinks, by adding asymmetry aromatic tetracarboxylic acid diester, can make the bending of polyamic acid molecule, produces snappiness.
And the coexistence effect of aromatic tetracarboxylic acid's derivative of above-mentioned symmetry and asymmetry can access performance most effectively when the two ratio of mixture as noted above.
(3) aromatic diamine
As aromatic diamine, can enumerate the compound that on an aromatic nucleus (phenyl ring etc.), has 2 amino, perhaps the aromatic nucleus more than 2 (phenyl ring etc.) with-O-,-S-,-CO-,-CH 2-,-SO-,-SO 2-wait base or the crosslinked compound of singly-bound with 2 amino.Specifically, for example, p-penylene diamines, o-penylene diamines, m-penylene diamines, 4,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino, two phenylcarbamoyls, 4,4 '-diaminodiphenylmethane, 1, two (4-amino-benzene oxygen) benzene of 4-etc.Wherein, preferred especially 4,4 '-diaminodiphenyl oxide.This is because by using these aromatic diamines, in more smooth the carrying out of reaction, can make more tough and the film of high heat resistance more.
(4) semi-conductivity high density polyimide precursor composition
Next, aromatic tetracarboxylic acid's diester and aromatic diamine are added with equimolar amount roughly be dissolved in the carbon black dispersion liquid that is obtained.
By above-mentioned aromatic tetracarboxylic acid's composition and organic diamine are made an addition in the carbon black dispersion liquid with equimolar amount roughly,, make semi-conductivity high density polyimide precursor composition by stirring and dissolving equably.Two kinds of composition uniform dissolution in carbon black dispersion liquid the time, also can heated (for example, about 40～70 ℃) as required.Known blending meanss such as use stirring are dissolved in the organic polar solvent two kinds of compositions and get final product.
The use level of modulation aromatic tetracarboxylic acid's diester and aromatic diamine, make and measure 100 weight parts with respect to the total of aromatic tetracarboxylic acid's diester and aromatic diamine, the carbon black in the carbon black dispersion liquid is that (about preferred 8～30 weight parts) get final product about 5～35 weight parts.Why use level in above-mentioned scope, is volume specific resistance (VR) and the surface resistivity (SR) that is in semiconductor regions in order to give to film.
The applicant thinks, above-mentioned semi-conductivity high density polyimide precursor composition, for example, in organic polar solvent, the ion pair of the carboxylic acid ion of aromatic tetracarboxylic acid's diester and the ammonium ion of aromatic diamine remains free state (for example with reference to following formula) in fact.
Figure A20048004293200461
(in the formula, Ar represents to remove 4 valency bases behind 2 carboxyls and 2 ester groups from the aromatic tetracarboxylic acid, and 2 divalent bases behind the amino are removed in Ar ' expression from aromatic diamine, and R represents alkyl.)
In addition, because come down to free state,, has the advantage that to do one's utmost to reduce employed quantity of solvent so be easy to be dissolved in the above-mentioned organic polar solvent.In addition, the non-volatile content concentration in the said composition can be set at: for example, about 35～60 weight %, the high density about preferred 40～60 weight %.CB concentration during this non-volatility is divided can be set at: for example, and about 4～30 weight %, about preferred 10～25 weight %.In addition, employed in this manual what is called " non-volatile content concentration " is meant the concentration of the method mensuration of being put down in writing with embodiment D-1.
In addition, in the scope that effect of the present invention is had no adverse effects, also can in above-mentioned composition, add glyoxaline compound (glyoxal ethyline, 1,2 dimethylimidazole, 2-methyl-4-methylimidazole, 2-ethyl-4-ethyl imidazol(e), 2-phenylimidazole), tensio-active agent additives such as (fluorine class tensio-active agents etc.).
Make dissolving of CB powder homodisperse and non-volatile content high density ground or dispersive semi-conductivity PI precursor composition like this.
In semi-conductivity high density PI precursor composition of the present invention, modulation CB powder disperses the carbon black dispersion liquid that forms equably, by aromatic tetracarboxylic acid's diester and aromatic diamine composition are dissolved in this carbon black dispersion liquid, the CB powder disperses equably, and the storage stability of CB powder homogeneously dispersed state significantly improves.And, the semi-conductivity PI precursor composition that uses it is rotated the resulting conductive poly imide pipe that is shaped, be endowed the electroconductibility that has the resistivity of very stable and homogeneous at its thickness direction.
Semi-conductivity high density PI precursor composition of the present invention is owing to dissolved monomer as shaping raw material, so non-volatile content concentration can significantly improve to 35～60 weight % in carbon black dispersion liquid.Therefore therefore, utilize semi-conductivity high density PI precursor composition of the present invention can easily make the thicker film of film, employed quantity of solvent is few, can suppress cost, makes the evaporation of solvent remove and becomes easy.
And semi-conductivity high density PI precursor composition of the present invention is because its viscosity also can be up to about 10～60 pools, so the PI film is difficult to be subjected to the influence of the centrifugal force of spinning-shaping.
D-2. semi-conductivity endless tubular polyimide film
Next, the manufacturing process to the semi-conductivity endless tubular PI film that uses above-mentioned synthetic semi-conductivity PI precursor composition is illustrated.
This manufacturing process adopts the method for rotary forming that uses rotor.At first semi-conductivity PI precursor composition is injected the inner face of rotor, evenly curtain coating is all in inner face.
The method of injection-curtain coating is, for example, and in the rotor that stops, inject to obtain final film thickness after the semi-conductivity PI precursor composition of suitable amount, slowly improve speed of rotation, up to the speed that centrifugal force works, all in inner face by the even curtain coating of centrifugal force.Perhaps, injection-curtain coating does not use centrifugal force passable yet.For example, the slot-shaped nozzle in that the inner face configuration of rotor is grown crosswise continues this cylinder of rotation lentamente, and this nozzle (with than this speed of rotation faster speed) also rotates.Then, the semi-conductivity PI precursor composition with shaping usefulness all sprays to this cylinder inner face equably from this nozzle.This cylinder mounting is on the rotation roller, and the rotation by this roller can be rotated indirectly.
Heating is for example to dispose thermal source such as far infra-red heater around this cylinder, carry out indirect heating from the outside.The size of this cylinder depends on the size of desirable semiconduction tubulose PI film.
Heating slowly heats up the cylinder inner face, at first is about 100～190 ℃, preferably reaches (the 1st heating phase) about 110 ℃～130 ℃.Heat-up rate for example gets final product about 1～2 ℃/min.Kept under said temperature 1～3 hour, and made only about half of above solvent evaporates, being shaped has self-supportive tubular film.In order to carry out imidization, need reach the temperature more than 280 ℃, but if heat with high like this temperature just beginning most, then not only polyimide shows high crystallization, influence the dispersion state of CB, and existence can't form tough problems such as overlay film.Therefore, as the 1st heating phase, ceiling temperature is the highest to be controlled at about 190 ℃, stops polycondensation under this temperature, just obtains tough tubulose PI film.
If next this stage, as the 2nd heating phase, heats in order to finish imidization after finishing, its temperature is (preferred about 300～380 ℃) about 280～400 ℃.At this moment neither reach this temperature suddenly from the 1st stage Heating temperature, to reach this temperature better but slowly heat up.
In addition, the 2nd stage heating can be directly carried out under the endless tubular film is attached to the state of rotor inner face, also can after the end of the 1st heating phase the endless tubular film be peeled off taking-up from rotor, other heater means that is used to reach imidization is provided, is heated to 280～400 ℃.The used time of this imidization, be about usually about 2～3 hours.Therefore, the required time of the 1st and the 2nd whole operations of heating phase was generally about 4～7 hours.
So just made semi-conductivity tubulose PI film of the present invention.Though there is no particular limitation for the thickness of this film, be generally about 30～200 μ m, be preferably about 60～120 μ m.During especially for the intermediate duplication band of electrofax mode, be preferably about 75～100 μ m.
The semi-conductivity of this film is that (resistance characteristic of (hereinafter referred to as " SR ") the two common decision of Ω/), this characteristic is to give by the blending dispersion of CB powder by volume specific resistance (Ω cm) (hereinafter referred to as " VR ") and surface resistivity.And the scope of this resistance, can freely change by the combined amount of CB powder basically.As the electrical resistivity range of film of the present invention, can illustratively be VR:10 2～10 14, SR:10 3～10 15,, can illustratively be VR:10 as preferable range 6～10 13, SR:10 7～10 14These electrical resistivity range can reach at an easy rate by the use level that adopts above-mentioned CB powder.In addition, the CB content in film of the present invention is generally about 5～25 weight %, is preferably about 8～20 weight %.
Semi-conductivity tubulose PI film of the present invention has the very resistivity of homogeneous.That is, the unique point of semi-conductivity tubulose PI film of the present invention is, the variability of the logarithm conversion value of surface resistivity SR and volume specific resistance VR is little, and in the full measuring point, the standard deviation of logarithm conversion value separately is in 0.2, and is preferred below 0.15 in film.In addition, have the little such feature of difference of the surface resistivity (logarithm conversion value) at the film surface and the back side, this difference is in 0.4, preferably in 0.2.And possess following feature: the logarithm conversion value LogSR of surface resistivity deducts the value of the logarithm conversion value LogVR of volume specific resistance, can maintain 1.0～3.0, preferred 1.5～3.0 such high values.
PI film of the present invention is because its excellent function such as resistance characteristic serves many purposes.For example, as the important use that needs charged characteristic, can enumerate the intermediate duplication band of the electrofax mode that is used for color printer, color copy machine etc. etc.As this band, necessary semi-conductivity (resistivity) for example is VR10 9～10 12, SR10 10～10 13, can use semi-conductivity endless tubular PI film of the present invention with being well suited for.
Semi-conductivity PI film of the present invention, the excellent performance as band has high yield strength (σ Y) and breaking tenacity (σ Cr).Yield strength (σ Y) more than 120MPa, 120～160MPa particularly, the ratio (σ of breaking tenacity and yield strength Cr/ σ Y) more than 1.10, particularly about 1.10～1.35.
Embodiment
Below jointly the present invention is done more detailed description, but the invention is not restricted to these embodiment with comparative example and embodiment.
A. first invention
By comparative example and embodiment more detailed description is done in first invention.
Yield strength described in this example (bending volt point stress), breaking tenacity, volume specific resistance (VR), surface resistivity (SR) and non-volatile content concentration are the following values of measuring.
[yield strength (MPa) (simply is σ Y) and breaking tenacity (MPa) (simply be σ Cr)]
The film that each example obtained is cut to wide 5mm, long 100mm, with it as test film, utilizing single shaft to distraction test machine (Shimadzu Scisakusho Ltd system odograph (odograph)), is to measure in 40mm, Deformation velocity 200mm/ minute with the distance drawn.Read σ from the S-S curve that is write down YAnd σ Cr
So-called this yield strength and breaking tenacity are very important strength factors in as the material design of band, and yield strength need be 120MPa at least.This is owing to can not the stress when being subjected to loading in assembling produce viscous deformation (dimensional change that causes because of extension).
In addition, breaking tenacity is bigger than yield strength also to be necessary, gives the anti-life-span (toughness) of the rotation of band.As its target, need σ at least Cr/ σ YMore than=1.10.
[VR and SR]
The tubular film that is obtained is cut to long 400mm as sample, use the resistance measurer " Hiresta IP-HR probe " of Mitsubishi chemical Co., Ltd's system, respectively on the width with equidistant mensuration 5 places and on vertical (week) direction with equidistant mensuration 8 places, add up to and measure 40 places, represent with all mean value.
VR measures after applying under the voltage of 100V through 10 seconds, and SR measures after applying under the 500V voltage through 10 seconds.
[non-volatile content concentration]
Sample (monomer mixture solution etc.) is placed heat resistance containers such as metal cup, and accurately weighing is made as Ag with sample weight at this moment.The heat resistance container that is placed with sample is put into electric oven, heated up in turn with 120 ℃ * 12 minutes, 180 ℃ * 12 minutes, 260 ℃ * 30 minutes and 300 ℃ * 30 minutes, and heat, drying, the weight (non-volatile content weight) of the solid state component that obtained is made as Bg.For same sample, measure the A and the B value (n=5) of 5 samples, in the substitution following formula (I), obtain non-volatile content concentration.The mean value that adopts these 5 samples is as the non-volatile content concentration among the present invention.
Non-volatile content concentration=B/A * 100 (%) (I)
Embodiment A-1
With 2,3,3 ', 4 '-biphenyltetracarboxyacid acid dimethyl ester (1 mole 2,3, the reactant of the methyl alcohol of 3 ', 4 '-biphenyl tetracarboxylic dianhydride and 2 moles, half ester) 716.0g (2.0 moles) and 4,4 '-diaminodiphenyl oxide 400.0g (2.0 moles) mix at normal temperatures and uniform dissolution in the nmp solvent of 1540g.This solution is that non-volatile content concentration is that 34.6 weight %, soltion viscosity are about 250mPas, do not have the stable solution of polycondensation, free state in fact.Below be referred to as " asymmetry monomer solution A ".
On the other hand, with 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dimethyl ester (1 mole 3,3 ', 4, the reactant of the methyl alcohol of 4 '-biphenyl tetracarboxylic dianhydride and 2 moles, half ester) 716.0g (2.0 moles) and 4,4 '-diaminodiphenyl oxide 400.0g (2.0 moles) mix at normal temperatures and uniform dissolution in the nmp solvent of 1540g.This solution is that non-volatile content concentration is that 34.6 weight %, soltion viscosity are about 250mPas, do not have the stable solution of polycondensation, free state in fact.Below be referred to as " symmetry monomer solution B ".
Then, for above-mentioned asymmetry monomer solution A and symmetry monomer solution B, with the amount ratio separately that EX.1 and EX.2 were put down in writing shown in the Table A-1, with fluorine class tensio-active agent (the Tohkem Products of Co., Ltd. makes EF-351) 0.037 weight % (to non-volatile content) thorough mixing, carry out deaeration.It is used monomer solution C as being shaped separately, from this this solution separately, take specified amount, inject in the rotor moulding separately under the following conditions.
Rotor: the metallic cylinder mounting that the inner face of internal diameter 100mm, wide 530mm is equipped with minute surface is configured to it and is in the state that rotates with the rotation of this roller on two rotation rollers.
Be shaped with the injection rate of monomer solution C: 45.9g
Heating temperature:, the interior surface temperature of this cylinder is controlled at 170 ℃ at the outer side of this cylinder configuration far infra-red heater.
At first, under the state that rotor stops, respectively this monomer solution of 45.9g is evenly injected this cylinder bottom surface.Then, begin rotation immediately, slowly improve speed, reach 24rad/s, evenly curtain coating begins heating in interior comprehensive.Heating is slowly to heat up to reach 170 ℃ when keeping this rotation, and heating is 90 minutes under this temperature.
90 minutes rotation-heating is cooled to normal temperature after finishing, and rotor is separated with keeping intact, is still in the hot blast detention baker (hotblast stove), begins to be used for the heating of imidization.This heating also is slowly to heat up to reach 350 ℃.Then, 30 minutes postcooling of heating are peeled off taking-up at the formed tubulose PI of this cylinder inner face film to normal temperature under this temperature.Each routine result is recorded in Table A-2.
Table A-1
EX No. The weight ratio of asymmetry monomer solution A and symmetry monomer solution B The mole % of asymmetry monomer solution A and symmetry monomer solution B CB powder amount (weight part) with respect to starting monomer 100 weight parts
Solution A Solution B Solution A Solution B
Embodiment A-1 1 200 200 50 50 0
2 80 320 20 80 0
Comparative examples A-1 3 280 120 70 30 0
4 40 360 10 90 0
5 0 200 0 100 0
6 200 0 100 0 0
Embodiment A-2 7 200 200 50 50 8.33
Comparative examples A-2 8 280 120 70 30 8.33
9 40 360 10 90 8.33
Table A-2
EX No. Thickness (μ m) Yield strength σ Y(MPa) Breaking tenacity σ cr(MPa) σ cr/σ Y VR(Ω·cm) SR(Ω/□) Remarks
Embodiment A-1 1 85 132.5 147 1.11 2.8×10 14 1.0×10 16
2 85 145 172.5 1.19 The same The same
Comparative examples A-1 3 85 123.5 123.5 1 The same The same
4 - - - - - - Crisp, can not measure
5 - - - - - - Crisp, can not measure
6 85 116 117.5 0.99 2.8×10 14 1.0×10 16
Embodiment A-2 7 85 131 144.5 1.1 3.0×10 10 1.4×10 12
Comparative examples A-2 8 85 119.5 120 1 4.2×10 10 5.0×10 12
9 - - - - - - Crisp, can not measure
Comparative examples A-1
The amount ratio of being put down in writing except the asymmetry monomer solution A that uses embodiment A-1 and symmetry monomer solution B, with EX.3～6 shown in the Table A-1 separately mixes, under the condition identical, form separately, imidization, from rotor, peel off, take out, measure with this example.Result separately is recorded in Table A-2.
Embodiment A-2
Use asymmetry monomer solution A and symmetry monomer solution B in the embodiment A-1, with the amount that EX.7 the was put down in writing ratio shown in the Table A-1, same with this example, at first behind the uniform mixing, (measure 100 weight parts to wherein adding CB powder (pH3, particle diameter 23nm) 14.0g with respect to full monomer total, be 8.33 weight parts), thorough mixing disperses in ball mill, last deaeration.It is used the semi-conductivity monomer solution as being shaped.Non-volatile content concentration in this semi-conductivity monomer solution is 36.8 weight %, and the CB concentration in this non-volatile content is 9.19 weight %.
Then, from this solution, take 45.9g, itself and embodiment A-1 are similarly injected in the rotor, after being shaped under the identical condition, carry out imidization.The imidization film that is obtained is peeled off from rotor, taken out, measure.The result is recorded in Table A-2.
Comparative examples A-2
Use the asymmetry monomer solution A and the symmetry monomer solution B of embodiment A-1, the amount ratio of being put down in writing with the EX.8,9 shown in the Table A-1 separately, same with this example, at first behind the uniform mixing, similarly measure the CB powder that 100 weight parts are 8.33 weight parts to wherein adding separately with embodiment A-2 with respect to full monomer total, thorough mixing disperses in ball mill, last deaeration.It is used the semi-conductivity monomer solution as being shaped.Non-volatile content concentration in this semi-conductivity monomer solution is 36.8 weight %, and the CB concentration in this non-volatile content is 9.19 weight %.
Then, from this solution A and B, respectively take 45.9g, similarly inject in the rotor, under identical condition, form with embodiment A-1.Behind the imidization, from rotor, peel off, take out, measure.Each result is recorded in Table A-2.
B. second invention
Next, with comparative example and embodiment more detailed description is done in second invention.
Embodiment B-1
With 2,3,3 ', 4 '-biphenyltetracarboxyacid acid dimethyl ester (1 mole 2,3,3 ', the reactant of the methyl alcohol of 4 '-biphenyltetracarboxyacid acid tetracarboxylic dianhydride and 2 moles, diester) 358.0g (1.0 moles) and 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dimethyl ester (1 mole 3,3 ', 4, the reactant of the methyl alcohol of 4 '-biphenyltetracarboxyacid acid tetracarboxylic dianhydride and 2 moles, diester) 358.0g (1.0 moles) and 4,4 '-diaminodiphenyl oxide 400.0g (2.0 moles) mixes down and is dissolved in equably in the nmp solvent of 1674g at 60 ℃, next, be warming up to 100 ℃ with 1hr, at 100 ℃ of heating 1hr postcooling.This solution is that non-volatile content concentration is that 32.9 weight %, number-average molecular weight are the solution of 2000 oligopolymer shape.Below be referred to as " oligopolymer mixed solution A ".
Add carbon black (CB) powder (pH3, particle diameter 23nm) 71.7g and NMP142.5g in this oligopolymer mixed solution A of 1000g, thorough mixing disperses in ball mill, last deaeration.It is used the semi-conductivity oligomer solution as being shaped.Non-volatile content concentration in this semi-conductivity oligomer solution is 33.0 weight %, and the CB concentration in this non-volatile content is 17.89 weight %.
Then, from this solution, take 109g, inject in the rotor, be shaped separately under the following conditions.
Rotor: the metallic cylinder mounting that the inner face of internal diameter 175mm, wide 540mm is equipped with minute surface is configured to it and is in the state that rotates with the rotation of this roller on two rotation rollers.
Heating temperature:, the interior surface temperature of this cylinder is controlled at 120 ℃ at the outer side of this cylinder configuration far infra-red heater.
At first, under the state of rotor rotation, this solution of 109g is uniformly coated on the cylinder inner face, begins heating.Heating is when keeping its rotation, and heating up with 2 ℃/min reaches 120 ℃, and heating is 90 minutes under this temperature.
After rotation, heating finish, do not cool off and directly rotor is separated, be still in the hot blast detention baker, begin to be used for the heating of imidization.This heating also is slowly to heat up to reach 320 ℃.Then, 30 minutes postcooling of heating are peeled off taking-up at the formed semi-conductivity tubulose of this cylinder inner face PI film to normal temperature under this temperature.In addition, the thickness of this film is 90 μ m.
In addition, the what is called in this specification sheets " non-volatile content concentration " is the following value of calculating.Sample (semi-conductivity oligomer solution etc.) is placed heat resistance container such as metal cup carry out accurate weighing, the sample weight of this moment is made as Ag.The heat resistance container that is placed with sample is put into electric oven, heated up in turn with 120 ℃ * 12 minutes, 180 ℃ * 12 minutes, 260 ℃ * 30 minutes and 300 ℃ * 30 minutes, and heat, drying, the weight (non-volatile content weight) of the solid state component that obtained is made as Bg.For same sample, measure the A of 5 samples and the value (n=5) of B, in the substitution following formula (I), obtain non-volatile content concentration.The mean value that adopts these 5 samples is as the non-volatile content concentration among the present invention.
Non-volatile content concentration=B/A * 100 (%) (I)
Reference example B-1
With the amount ratio identical with Embodiment B-1, carboxylic acid dimethyl ester and diaminodiphenyl oxide are mixed, will directly cool off at 60 ℃ of following dissolved solution.This solution is that non-volatile content concentration is 32.9 weight %, is essentially the solution of free state.Below be referred to as " monomer solution A ".
Add CB powder (pH3, particle diameter 23nm) 31.0g and NMP60.0g in this monomer solution of 1000g A, thorough mixing disperses in ball mill, last deaeration.It is used the semi-conductivity monomer solution as being shaped.The concentration of the non-volatile content in this semi-conductivity monomer solution is 33.0 weight %, and the CB concentration in this non-volatile content is 8.61 weight %.
Then, from this solution, take 109g, below, similarly heat shaping with Embodiment B-1, peel off and take out semi-conductivity tubulose PI film.In addition, the thickness of this film is 92 μ m.
Embodiment B-2
With 2,3,3 ', 4 '-biphenyltetracarboxyacid acid dimethyl ester (1 mole 2,3,3 ', the reactant of the methyl alcohol of 4 '-biphenyltetracarboxyacid acid tetracarboxylic dianhydride and 2 moles, diester) 143.2g (0.4 mole) and 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dimethyl ester (1 mole 3,3 ', 4, the reactant of the methyl alcohol of 4 '-biphenyltetracarboxyacid acid tetracarboxylic dianhydride and 2 moles, diester) 572.8g (1.6 moles) and 4,4 '-diaminodiphenyl oxide 400g (2 moles) mixes down and is dissolved in equably in the nmp solvent of 1674g at 60 ℃, next, be warming up to 110 ℃ with 1hr, heat the 1hr postcooling down at 110 ℃.This solution is that non-volatile content concentration is that 32.9 weight %, number-average molecular weight are the solution of 4000 oligopolymer shape.Below be referred to as " oligopolymer mixing solutions B ".
Add CB powder (pH3, particle diameter 23nm) 78.9g and NMP157.1g in this oligopolymer mixing solutions of 1000g B, thorough mixing disperses in ball mill, last deaeration.It is used the semi-conductivity oligomer solution as being shaped.Non-volatile content concentration in this semi-conductivity oligomer solution is 33.0 weight %, and the CB concentration in this non-volatile content is 19.34 weight %.
Then, from this solution, take 109g, inject in the rotor, below, similarly heat shaping with Embodiment B-1, peel off and take out semi-conductivity tubulose PI film.In addition, the thickness of this film is 89 μ m.
Comparative example B-1
With the amount ratio identical with Embodiment B-1, carboxylic acid dimethyl ester and diaminodiphenyl oxide are mixed, 60 ℃ of dissolvings down, next be warming up to 130 ℃ with 1hr, heat the 1hr postcooling down at 130 ℃.But cooled this solution becomes the gelatinous solid that muddiness takes place, and can not be used for being shaped.
This gel promptly uses solvent cut to dissolve again.Measure the imidization rate of the gel that is obtained, results verification has carried out about 35% imidization reaction.That is, the applicant thinks, because Heating temperature height, imidization reaction are excessive, so solubleness reduces, separated out resinous principle.
Test routine B-1
The film of the foregoing description B-1～B-2, reference example B-1 and comparative example B-1 is created conditions and the measurement result of the resistance value of the film that obtained, is shown in table B-1.Average, the standard deviation of the surface resistivity of table among the B-1, volume specific resistance is all with the logarithm conversion value representation.
[number-average molecular weight]
Number-average molecular weight is to be measured by GPC method (solvent: NMP, polyethylene oxide convert).
[imidization rate]
By in infrared spectrophotometer, being derived from the absorption (1780cm of imide -1) and be derived from the absorption (1510cm of phenyl ring -1) the ratio of intensity calculate.Because the absorption of phenyl ring does not still change behind imidization at precursor, so it is used in contrast.
[mensuration of surface resistivity (SR) and volume specific resistance (VR)]
The tubular film that is obtained is cut to long 400mm as sample, use the resistance measurer " Hiresta IP-HR probe " of Mitsubishi chemical Co., Ltd's system, on the width with equidistant mensuration 3 places and on vertical (week) direction with equidistant mensuration 4 places, add up to and measure 12 places, represent with all mean value.
Volume specific resistance (VR) is to measure after applying under the voltage of 100V through 10 seconds, and surface resistivity (SR) is to measure after applying under the voltage of 500V through 10 seconds.
Table B-1
Heating temperature Number-average molecular weight The imidization rate The ratio of asymmetric gonosome and symmetrical gonosome CB powder amount in the film Thickness The sheet resistance value of film face side (LogSR) The sheet resistance value of film rear side Volume specific resistance (LogVR) The table back of the body of surface resistivity is poor LogSR-LogVR
Asymmetric gonosome The symmetry gonosome On average On average Standard deviation On average Standard deviation On average Standard deviation
Embodiment B-1 100℃ 2000 10％ 50 50 17.89 90μm 11.77 0.11 11.87 0.09 9.88 0.11 0.10 1.89
Embodiment B-2 110℃ 4000 20％ 20 80 19.34 89μm 11.93 0.11 12.07 0.13 10.49 0.08 0.14 1.44
Reference example B-1 60℃ 250 0％ 50 50 8.61 92μm 11.99 0.30 12.40 0.25 12.10 0.43 0.41 -0.11
Comparative example B-1 130℃ 35％ 50 50
The mean value of surface resistivity and volume specific resistance, standard deviation are the logarithm conversion values
Resistance measurement: bandwidth direction 3 points * Zhou Fangxiang 4 point=12 point
Apply voltage: the value of 100V after 10 seconds
Resistance measurement machine: Hiresta IP HR プ ロ one Block
By table B-1 as can be known, the film of embodiment, with respect to reference example and comparative example, the standard deviation of surface resistivity and volume specific resistance is very little, and promptly variability is little.
In addition, the film of embodiment, with respect to reference example and comparative example, the difference of the surface resistivity of film face side and rear side (logarithm conversion value) is very little, and the intermediate duplication band as color copy machine is used has good characteristic.
In addition, in general, if the heat temperature raising speed in quickening to be shaped, then the logarithm conversion value LogSR of the surface resistivity value (Log (SR/VR)) that deducts the logarithm conversion value LogVR of volume specific resistance will reduce, therefore, when using as replication band, it is electric, charged that removing of electric charge can not be correctly carried out in existence, becomes the such problem of the bad reason of image.But, as can be known by using the oligopolymer mixing solutions, just this value can be maintained high value (1.0～3.0), just can further improve the productivity of film thus.
C. the 3rd invention
Next, utilize comparative example and embodiment that the 3rd invention is described in more detail.In addition, below, with " a-BPDA " expression 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride is with " s-BPDA " expression 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride.Number-average molecular weight is by GPC method (solvent: NMP) measure.
Embodiment C-1
Methyl alcohol 22.8g, N-N-methyl-2-2-pyrrolidone N-160g are dropped into the a-BPDA of 14g and the s-BPDA of 56g (20 moles of %: 80 moles of %), under 70 ℃ bath temperature, react under the nitrogen circulation.Next, be cooled to 65 ℃ of bath temperatures after, drop into 4 of 47.6g, 4 '-diaminodiphenyl oxide (ODA) slowly stirs, and obtains nylon salt type monomer solution 300.4g.The viscosity of this solution is 1.8 pools, and the concentration of non-volatile content is 36.3 weight %.
Next, add the ODA of 47.6g among the N-N-methyl-2-2-pyrrolidone N-448g under the nitrogen circulation, 50 ℃ of insulations, stirring is dissolved it fully.In this solution, slowly add the powder that has mixed a-BPDA:35g and s-BPDA:35g, obtain polyamic acid solution 605.6g.The number-average molecular weight of this polyamic acid solution is 16000, viscosity is 30 pools, non-volatile content concentration is 18.0 weight %.
Made and mixed the polyimide precursor solution 180g that above-mentioned nylon salt type monomer solution 100g and polyamic acid solution 80g form.Viscosity is 13 pools, and non-volatile content concentration is 28.2 weight %.
In this precursor solution of 150g, add acid carbon (pH3.0) 7.5g and N-N-methyl-2-2-pyrrolidone N-16.7g, in ball mill, carry out the sooty homodisperse.The non-volatile content concentration of this masterbatch solution is 28.6 weight %, and the CB concentration in this non-volatile content is 15.1 weight %, and the sooty median size is 0.28 μ m, and maximum particle diameter is 0.58 μ m.In addition, the sooty median size after 10 days is 0.28 μ m, and maximum particle diameter is 0.76 μ m, does not almost change.
In addition, the what is called in this specification sheets " non-volatile content concentration " is the following value that calculates.Sample (nylon salt type monomer solution etc.) is placed heat resistance container such as metal cup carry out accurate weighing, with the sample weight of this moment as Ag.The heat resistance container that is placed with sample is put into electric oven, heated up in turn with 120 ℃ * 12 minutes, 180 ℃ * 12 minutes, 260 ℃ * 30 minutes and 300 ℃ * 30 minutes, and heat, drying, with the weight (non-volatile content weight) of the solid state component that obtained as Bg.For same sample, measure the A and the B value (n=5) of 5 samples, in the substitution following formula (I), obtain non-volatile content concentration.The mean value that adopts these 5 samples is as the non-volatile content concentration among the present invention.
Non-volatile content concentration=B/A * 100 (%) (I)
Embodiment C-2
Methyl alcohol 22.8g, N-N-methyl-2-2-pyrrolidone N-160g are dropped into the a-BPDA of 35g and the s-BPDA of 35g (50 moles of %: 50 moles of %), under 80 ℃ bath temperature, react under the nitrogen circulation.Next, be cooled to 65 ℃ of bath temperatures after, drop into 4 of 47.6g, 4 '-diaminodiphenyl oxide (ODA) slowly stirs, and obtains nylon salt type monomer solution 300.4g.The viscosity of this solution is 1.8 pools, and the concentration of non-volatile content is 36.3 weight %.
Next, the ODA of interpolation 47.6g in nitrogen circulation N-N-methyl-2-2-pyrrolidone N-448g down, 50 ℃ of insulations are stirred it are dissolved fully.In this solution, slowly add s-BPDA:70g, obtain polyamic acid solution 605.6g.The number-average molecular weight of this polyamic acid solution is 12000, viscosity is 12 pools, non-volatile content concentration is 18.0 weight %.
Made and mixed the polyimide precursor solution 180g that above-mentioned nylon salt type monomer solution 100g and polyamic acid solution 80g form.Viscosity is 5.2 pools, and non-volatile content concentration is 28.2 weight %.
In this precursor solution 150g, add acid carbon (pH3.0) 7.5g and N-N-methyl-2-2-pyrrolidone N-16.7g, in ball mill, carry out the sooty homodisperse.The non-volatile content concentration of this masterbatch solution is 28.6 weight %, and the CB concentration in this non-volatile content is 15.1 weight %, and the sooty median size is 0.31 μ m, and maximum particle diameter is 0.77 μ m.In addition, the sooty median size after 10 days is 0.31 μ m, and maximum particle diameter is 0.88 μ m, does not almost change.
Embodiment C-3
Methyl alcohol 22.8g, N-N-methyl-2-2-pyrrolidone N-250g are dropped into the a-BPDA of 21g and the s-BPDA of 49g (30 moles of %: 70 moles of %), under 80 ℃ bath temperature, react under the nitrogen circulation.Next, be cooled to 65 ℃ of bath temperatures after, drop into 4 of 47.6g, 4 '-diaminodiphenyl oxide (ODA) slowly stirs, and obtains nylon salt type monomer solution 390.4g.The viscosity of this solution is 0.7 pool, and non-volatile content concentration is 27.9 weight %.
(number-average molecular weight is 21000 to have made mixed polyamide imide solution in this nylon salt type monomer solution 200g (VYLOMAX HR-16NN Toyo Boseki K.K system), solid state component is 14 weight %, and viscosity is 500 pools) the polyimide precursor solution 310g that forms of 110g.Viscosity is 18 pools, and non-volatile content concentration is 23.0 weight %.
In this precursor solution 260g, add acid carbon (pH3.0) 10.9g and N-N-methyl-2-2-pyrrolidone N-25.2g, in ball mill, carry out the sooty homodisperse.The non-volatile content concentration of this masterbatch solution is 23.9 weight %, and the carbon black concentration in this non-volatile content is 15.4 weight %, and the sooty median size is 0.215 μ m, and maximum particle diameter is 0.51 μ m.In addition, the sooty median size after 10 days is 0.218 μ m, and maximum particle diameter is 0.58 μ m, does not almost change.
Reference example C-1
In the nylon salt type monomer of 200g Embodiment C-1 made, add acid carbon (pH3.0) 13.5g and organic solvent (NMP) 120g, in ball mill, lead dispersion.The viscosity of this solution is 5 pools, and non-volatile content concentration is 25.8 weight %, and the CB concentration in this non-volatile content is 15.7 weight %, and the sooty median size is 0.39 μ m, and maximum particle diameter is 2.26 μ m.And the sooty median size after 10 days is 0.79 μ m, and maximum particle diameter is 7.70 μ m, has confirmed the sooty cohesion.
Reference example C-2
The ODA of interpolation 47.6g in nitrogen circulation N-N-methyl-2-2-pyrrolidone N-450g down, 50 ℃ of insulations, and stir it is dissolved fully.In this solution, slowly add s-BPDA:70g, obtain polyamic acid solution 567.6g.The weight-average molecular weight of this polyamic acid solution is 5000, viscosity is 6.6 pools, non-volatile content concentration is 19.2 weight %.Make the polyimide precursor solution 180g that the nylon salt type monomer 100g that mixes this solution 80g and Embodiment C-2 made forms, added acid carbon (pH3.0) 9.5g and organic solvent (NMP) 120g, in ball mill, led dispersion.The viscosity of this solution is 6 pools, and non-volatile content concentration is 19.8 weight %, and the CB concentration in this non-volatile content is 15.5 weight %, and the sooty median size is 0.26 μ m, and maximum particle diameter is 0.87 μ m.And the sooty median size after 10 days is 0.77 μ m, and maximum particle diameter is 5.10 μ m, has confirmed the sooty cohesion.
Embodiment C-4 (making of the tubular polyimide class film that is undertaken by the spinning-shaping method)
With the cylindric mould of the speed of rotation of 100rpm (10.5rad/s) rotation external diameter 300mm, internal diameter 270mm, long 500mm, evenly be coated with Embodiment C-1, C-2, the C-3 of wide 480mm, the solution of reference example C-1, C-2 at the inner face of this cylinder mould simultaneously.Coating thickness is calculated by non-volatile content concentration, makes that the thickness of polyimide band is 100 μ m.Solvent evaporates is, is warming up to 110 ℃ with 60 minutes, keeps 120 minutes at 110 ℃ afterwards, carries out solvent evaporates, made to have self-supportive pipe.
Next, the state that is attached to cylindric mold inside with this pipe drops in the high-temperature heater, is warming up to 320 ℃ with 120 minutes, 320 ℃ of heating 60 minutes down, carries out the polyimide conversion.Then, be cooled to normal temperature, tubular polyimide class film is taken out from mould.Its condition of surface is judged with naked eyes.
The mensuration of surface resistivity (SR) and volume specific resistance (VR) is, the polyimide pipe that is obtained is cut to long 400mm as sample, use the resistance measurer " Hiresta IP-HR probe " of Mitsubishi chemical Co., Ltd's system, on the width with equidistant mensuration 3 places and on vertical (week) direction with equidistant mensuration 4 places, add up to and measure 12 places, represent with all mean value.
Volume specific resistance (VR) is to measure after applying under the voltage of 100V through 10 seconds, and surface resistivity (SR) is to measure after applying under the voltage of 500V through 10 seconds.
Measurement result is summarized among the table C-1.Average, the standard deviation of the surface resistivity among the table C-1, volume specific resistance all are to represent with the logarithm conversion value.In addition, the thickness of the CB content in the pipe and this pipe also-and be shown in table C-1.
Table C-1
Embodiment C-1 Embodiment C-2 Embodiment C-3 Reference example C-1 Reference example C-2
Condition of surface Well Well Well Condensation product is arranged Condensation product is arranged
Surface resistivity Log (Ω/) On average 10.28 10.51 10.34 7.01 8.84
Standard deviation 0.15 0.07 0.03 0.05 0.10
Back side resistivity Log (Ω/) On average 10.31 10.53 10.37 8.83 10.28
Standard deviation 0.14 0.07 0.03 0.61 0.14
Volume specific resistance Log (Ω cm) On average 8.63 8.63 8.92 9.64 8.7
Standard deviation 0.07 0.04 0.06 0.26 0.2
(back side-surface) resistivity Index 0.02 0.02 0.03 1.82 1.44
(surface-volume) resistivity Index 1.66 1.88 1.42 -2.62 0.14
CB content (weight %) 15.1 15.1 15.4 15.7 15.5
Mean thickness (μ m) 100 100 100 100 100
By table C-1 as can be known, the pipe of embodiment, with respect to reference example, the standard deviation of surface resistivity and volume specific resistance is very little, and promptly variability is little.
In addition, the pipe of embodiment, with respect to reference example, the difference of the surface resistivity of pipe face side and rear side (logarithm conversion value) is very little, as the replication band of electrofax mode, has good characteristic.
And, in general, if the heat temperature raising speed in quickening to be shaped, then the logarithm conversion value LogSR of the surface resistivity value (Log (SR/VR)) that deducts the logarithm conversion value LogVR of volume specific resistance will reduce, therefore, when using as replication band, it is electric, charged that removing of electric charge can not be correctly carried out in existence, becomes the such problem of the bad reason of image.But the semi-conductivity PI precursor composition of the application of the invention just can maintain this value high value (1.0～2.0) as can be known.
Relative therewith, in reference example, be the value of the surface resistivity of pipe less than back side resistivity, the applicant thinks to have produced the sooty concentration gradient on the thickness direction of pipe.Its result increases for the value of volume specific resistance as can be known, and variability has also increased.
D. the 4th invention
Next, utilize comparative example and embodiment that more detailed description is done in the 4th invention.Below, with " a-BPDA " expression 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride is with " s-BPDA " expression 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride.
Embodiment D-1
The acid carbon of 27g (pH3.0, volatile matter 14.5%) is added in the 153g organic polar solvent N-N-methyl-2-2-pyrrolidone N-, pre-dispersed after, in ball mill, lead dispersion.The sooty median size is 0.29 μ m, and maximum particle diameter is 0.55 μ m.Next, in this solution of 120g, drop into the a-BPDA of 14g and s-BPDA, the methyl alcohol 22.8g of 56g, under 60 ℃ bath temperature, reaction under the nitrogen circulation.
Next, be cooled to 50 ℃ of bath temperatures after, drop into 4 of 47.6g, 4 '-diaminodiphenyl oxide (ODA) slowly stirs, and obtains the carbon black dispersion high density polyimide precursor composition 260g that is made of monomer.The viscosity of this solution is 32 pools, and non-volatile content concentration is 48.9 weight %, and the CB concentration in this non-volatile content is 14.2 weight %, and the sooty median size is 0.29 μ m, and maximum particle diameter is 0.58 μ m.In addition, the sooty median size after 10 days is 0.31 μ m, and maximum particle diameter is 0.67 μ m, does not almost change.
In addition, the what is called in this specification sheets " non-volatile content concentration " is the following value that calculates.Sample (carbon black dispersion high density polyimide precursor composition etc.) is placed heat resistance container such as metal cup carry out accurate weighing, with the sample weight of this moment as Ag.The heat resistance container that is placed with sample is put into electric oven, heated up in turn with 120 ℃ * 12 minutes, 180 ℃ * 12 minutes, 260 ℃ * 30 minutes and 300 ℃ * 30 minutes, and heat, drying, with the weight (non-volatile content weight) of the solid state component that obtained as Bg.For same sample, measure the A and the B value (n=5) of 5 samples, in the substitution following formula (I), obtain non-volatile content concentration.The mean value that adopts these 5 samples is as the non-volatile content concentration among the present invention.
Non-volatile content concentration=B/A * 100 (%) (I)
Embodiment D-2
10g furnace black (pH9.0, volatile matter 1.5%) is added in the 120g organic polar solvent N-N-methyl-2-2-pyrrolidone N-, pre-dispersed after, in ball mill, lead dispersion.The sooty median size is 0.67 μ m, and maximum particle diameter is 3.92 μ m.Next, in this solution of 125g, drop into the a-BPDA of 35g and s-BPDA, the methyl alcohol 22.8g of 35g, under 70 ℃ bath temperature, reaction under the nitrogen circulation.Next, be cooled to 50 ℃ of bath temperatures after, drop into 4 of 47.6g, 4 '-diaminodiphenyl oxide (ODA) slowly stirs, and obtains the carbon black dispersion high density polyimide precursor composition 265g that is formed by monomer.The viscosity of this solution is 12 pools, and non-volatile content concentration is 44.7 weight %, and the CB concentration in the non-volatile content is 8.2 weight %, and the sooty median size is 0.77 μ m, and maximum particle diameter is 3.92 μ m.And the sooty median size after 10 days is 0.77 μ m, and maximum particle diameter is 4.47 μ m, does not almost change.
Comparative Example D-1
With the acid carbon (pH3.0 of 20g, volatile matter 14.5%) be added into 600g by in s-BPDA and the ODA institute synthetic high-molecular weight polyamic acid solution (viscosity is 50 pools, and non-volatile content concentration is 18.0 weight %), in ball mill, lead dispersion, the tackify rate height of solution becomes gel.Next, in this solution, add the organic solution (NMP) of 300g, carry out redispersion.The viscosity of this solution is 8 pools, and non-volatile content concentration is 13.9 weight %, and the CB concentration in the non-volatile content is 15.6 weight %, and the sooty median size is 0.32 μ m, and maximum particle diameter is 0.77 μ m.And the sooty median size after 10 days is 0.32 μ m, and maximum particle diameter is 0.77 μ m, does not almost change.
Reference example D-1
Methyl alcohol 22.8g, N-N-methyl-2-2-pyrrolidone N-160g are dropped into the a-BPDA of 35g and the s-BPDA of 35g (50 moles of %: 50 moles of %), under 70 ℃ bath temperature, react under the nitrogen circulation.Next, be cooled to 60 ℃ of bath temperatures after, drop into 4 of 47.6g, 4 '-diaminodiphenyl oxide (ODA) slowly stirs, and obtains nylon salt type monomer solution 300.4g.The viscosity of this solution is 1.8 pools, and non-volatile content concentration is 36.3 weight %.Add acid carbon (pH3.0, volatile matter 14.5%) of 16.5g and 140g organic solvent (NMP) to this solution, in ball mill, lead dispersion.The viscosity of this solution is 5 pools, and non-volatile content concentration is 27.5 weight %, and the CB concentration in the non-volatile content is 12.3 weight %, and the sooty median size is 0.47 μ m, and maximum particle diameter is 1.73 μ m.And the sooty median size after 10 days is 0.78 μ m, and maximum particle diameter is 5.12 μ m, has confirmed the sooty cohesion.
Embodiment D-3 (making of the tubular polyimide film that is undertaken by the spinning-shaping method)
With the cylindric mould of the speed of rotation of 100rpm (10.5rad/s) rotation external diameter 300mm, internal diameter 270mm, long 500mm, evenly be coated with the solution of embodiment D-1, the D-2 of wide 480mm and Comparative Example D-1, reference example D-1 simultaneously at the inner face of this cylinder mould.Coating thickness is calculated by non-volatile content concentration, makes that the thickness of polyimide band is 100 μ m.The volatilization of solvent is to be warming up to 100 ℃ with 60 minutes, and afterwards with the solvent evaporates of visual inspection under 100 ℃, mensuration makes solvent evaporates finish the needed time.
Next, the state that is attached to cylindric mold inside with this pipe drops in the high-temperature heater, is warming up to 320 ℃ with 120 minutes, 320 ℃ of following heat 60 minutes, carries out the polyimide conversion.Then, be cooled to normal temperature, tubular polyimide film is taken out from mould.More than the results are shown in table D-1.In addition, the thickness of the CB content in the pipe and this tubular film also is shown in table D-1 in the lump.
In addition, the mensuration of surface resistivity (SR) is, the tubular polyimide film that is obtained is cut to long 400mm as sample, use the resistance measurer " Hiresta IP-HR probe " of Mitsubishi chemical Co., Ltd's system, on the width with equidistant mensuration 3 places and on vertical (week) direction with equidistant mensuration 4 places, add up to and measure 12 places, represent with all mean value.Surface resistivity (SR) is to measure after applying under the voltage of 500V through 10 seconds.
Table D-1
Shaping solution The time that solvent evaporates is required Condition of surface Surface resistivity (Ω/) CB content (weight %) in the pipe The thickness of pipe (μ m)
Embodiment D-1 45 minutes Well 2.5×10 10 14.2 94～102
Embodiment D-2 60 minutes Well 5.0×10 7 8.1 96～103
Comparative Example D-1 170 minutes Well 2.0×10 10 15.6 88～102
Reference example D-1 110 minutes The carbon condensation product is arranged 2.0×10 6 12.3 95～104
In existing method (comparative example), the non-volatile content concentration of shaping raw material is low, for the organic polar solvent that volatilizees a large amount of needs a lot of time, the non-constant of production efficiency.In addition, adding in monomer solution etc., disperseing in the method for CB, the heating when disperseing makes the reaction of monomer solution to carry out, the solution state instability.
The effect of invention
Tubulose PI film of the present invention can be made the tubular polyimide film of the endless (do not have connect seam) of high-quality non-conductive or semi-conductivity easy, efficient and economically.
Specifically, according to first invention,, can obtain direct endless tubular PI film by the polyimide raw material monomer that constitutes by specific composition and the combination of method of rotary forming.In addition, compare, shortened the time greatly with the manufacture method of present endless tubular PI film via polyamic acid.In addition, because of the greatly rationalization of process management,, also can obtain more stable high-quality tubulose PI film improving the productive while.The endless tubular PI film that is obtained can be used in various uses, especially, semiconduction endless tubular film, as intermediate duplication band of the electrofax mode that for example is used for color printer, color copy machine etc. etc., can be more suitable.
The semi-conductivity tubulose PI film of second invention is owing to use aromatic tetracarboxylic acid's composition and aromatic diamine composition with regulation to carry out the resulting aromatic amides acid oligomer of polycondensation as shaping raw material, so have the resistivity of homogeneous.Promptly, semi-conductivity tubulose PI film of the present invention has following excellent specific property: the variability of surface resistivity and volume specific resistance is little, the difference of the surface resistivity (logarithm conversion value) at the surface, film surface and the back side is little, and the value that the logarithm conversion value LogSR of surface resistivity deducts the logarithm conversion value LogVR of volume specific resistance can maintain high value (1.0～3.0).Therefore, semi-conductivity tubulose PI film of the present invention for example can be suitable as in the color copy machine etc. employed intermediate duplication band etc. and since can carry out electric charge rightly remove electricity, charged, so just can carry out the picture processing of excellence.
The semi-conductivity tubulose PI class film of the 3rd invention, resulting semiconductive polyimide class precursor composition uses as shaping raw material in the mixing solutions that is made of nylon salt type monomer solution and high molecular polyimide precursor solution or superpolyamide imide solution because carbon black is dispersed in, so have the resistivity of homogeneous.That is, semi-conductivity tubulose PI class film of the present invention has following excellent specific property: the variability of surface resistivity and volume specific resistance is little, and the difference of the surface resistivity (logarithm conversion value) at the surface, film surface and the back side is little.Therefore, semi-conductivity tubulose PI class film of the present invention can be suitable as the intermediate duplication band of color electronography mode for example etc. and since can carry out electric charge rightly remove electricity, charged, so just can carry out the picture processing of excellence.
In the semi-conductivity high density PI precursor composition of the 4th invention, the CB powder disperses equably, and the storage stability of CB powder homogeneously dispersed state is very high.And, the semi-conductivity PI precursor composition that has used it is rotated the conductive tubular PI film that shaping obtains, be endowed the electroconductibility that has the resistivity of highly stable and homogeneous at its thickness direction.That is, under situation as the intermediate duplication band of employed electrofax mode in for example color printer, the color copy machine etc. etc. since can carry out electric charge rightly remove electricity, charged, so just can carry out the picture processing of excellence.In addition, semi-conductivity high density PI precursor composition of the present invention is owing to the monomer that has dissolved in carbon black dispersion liquid as shaping raw material, so non-volatile content concentration can be brought up to about 35～60 weight %.Therefore, utilize semi-conductivity high density PI precursor composition of the present invention, can easily make the thicker film of film,,, make the evaporation of solvent remove more easy so can suppress cost because employed quantity of solvent is few.

Claims (32)

1. an endless tubular polyimide film is characterized in that,
Constitute by polyimide, this polyimide is that the aromatic tetracarboxylic acid's composition more than 2 kinds that the mixture by 85～45 moles of % of 15～55 moles of % of asymmetry aromatic tetracarboxylic acid composition and symmetry aromatic tetracarboxylic acid composition constitutes becomes branch to form with aromatic diamine
Its yield strength (σ Y) be more than the 120MPa, the ratio (σ of breaking tenacity and yield strength Cr/ σ Y) be more than 1.10.
2. a semi-conductivity endless tubular polyimide film is characterized in that,
Disperse black carbon forms in aromatic tetracarboxylic acid's composition more than 2 kinds that the mixture by 15～55 moles of % of asymmetry aromatic tetracarboxylic acid composition and 85～45 moles of % of symmetry aromatic tetracarboxylic acid composition constitutes and the formed polyimide of aromatic diamine composition, and its surface resistivity is 10 3～10 15Ω/.
3. semi-conductivity endless tubular polyimide film as claimed in claim 2, it is characterized in that, the standard deviation of the logarithm conversion value of surface resistivity is in 0.2, the standard deviation of the logarithm conversion value of volume specific resistance is in 0.2, and the difference of the logarithm conversion value of surface resistivity and the logarithm conversion value of back side resistivity is in 0.4.
4. the manufacture method of an endless tubular polyimide film is characterized in that,
Aromatic tetracarboxylic acid's composition that will be made of asymmetry aromatic tetracarboxylic acid or 15～55 moles of % of its ester and symmetry aromatic tetracarboxylic acid or 85～45 moles of % of its ester and aromatic diamine composition mix the formed mixing solutions that is essentially free state with equimolar amount roughly, be configured as pipe with the spinning-shaping method, carry out heat treated, imidization.
5. the manufacture method of a semi-conductivity endless tubular polyimide film is characterized in that,
The aromatic tetracarboxylic acid's composition that constitutes by asymmetry aromatic tetracarboxylic acid or 15～55 moles of % of its ester and symmetry aromatic tetracarboxylic acid or 85～45 moles of % of its ester and aromatic diamine composition with the mixing solutions that is essentially free state that roughly equimolar amount mixes in, total with respect to aromatic tetracarboxylic acid's composition and aromatic diamine composition is measured 100 weight parts, the carbon black that disperses 1～35 weight part, the monomer mixture solution of formed semi-conductivity is configured as pipe with the spinning-shaping method, carry out heat treated, imidization.
6. semi-conductivity endless tubular polyimide film by the intermediate duplication band of the electrofax mode that is used for of the described manufacture method manufacturing of claim 5.
7. a semi-conductivity aromatic amides acid composition is characterized in that,
Contain by the aromatic tetracarboxylic acid's composition more than 2 kinds and aromatic diamine and carry out aromatic amides acid oligomer, carbon black and the organic polar solvent that polycondensation was obtained with equimolar amount roughly.
8. semi-conductivity aromatic amides acid composition as claimed in claim 7, it is characterized in that, described aromatic amides acid oligomer is to carry out the aromatic amides acid oligomer that polycondensation was obtained under the temperature in organic polar solvent, below about 80 ℃ of equimolar amount roughly by the aromatic tetracarboxylic acid's dianhydride more than 2 kinds and aromatic diamine.
9. semi-conductivity aromatic amides acid composition as claimed in claim 8, it is characterized in that, aromatic tetracarboxylic acid's dianhydride more than 2 kinds is by 15～55 moles of % of asymmetry aromatic tetracarboxylic acid dianhydride and 85～45 moles of mixtures that % constituted of symmetry aromatic tetracarboxylic acid dianhydride.
10. semi-conductivity aromatic amides acid composition as claimed in claim 7, it is characterized in that, described aromatic amides acid oligomer is to carry out the aromatic amides acid oligomer that polycondensation was obtained by the aromatic tetracarboxylic acid's diester more than 2 kinds and aromatic diamine with equimolar amount roughly in organic polar solvent, under the temperature about 90～120 ℃.
11. semi-conductivity aromatic amides acid composition as claimed in claim 10, it is characterized in that, aromatic tetracarboxylic acid's diester more than 2 kinds is by 15～55 moles of % of asymmetry aromatic tetracarboxylic acid diester and 85～45 moles of mixtures that % constituted of symmetry aromatic tetracarboxylic acid diester.
12. semi-conductivity aromatic amides acid composition as claimed in claim 7 is characterized in that the number-average molecular weight of described aromatic amides acid oligomer is about 1000～7000.
13. semi-conductivity aromatic amides acid composition as claimed in claim 7 is characterized in that, measures 100 weight parts with respect to the total of aromatic tetracarboxylic acid's composition and organic diamine, the sooty use level is about 3～30 weight parts.
14. the manufacture method of a semi-conductivity endless tubular polyimide film is characterized in that, the described semi-conductivity aromatic amides of claim 7 acid composition is rotated shaping, heat treated.
15. semi-conductivity endless tubular polyimide film by the intermediate duplication band of the electrofax mode that is used for of the described manufacture method manufacturing of claim 14.
16. the manufacture method of a semi-conductivity aromatic amides acid composition is characterized in that,
In organic polar solvent, aromatic tetracarboxylic acid's composition more than 2 kinds and aromatic diamine carry out the part polycondensation with equimolar amount roughly, become aromatic amides acid oligomer solution, with this aromatic amides acid oligomer solution and conductive carbon black powder uniform mixing.
17. a semiconductive polyimide class precursor composition is characterized in that,
Aromatic tetracarboxylic acid's diester more than 2 kinds and aromatic diamine are being dissolved in the nylon salt type monomer solution that forms in the organic polar solvent with equimolar amount roughly, mix high-molecular weight polyimide precursor solution or high-molecular weight polyamidoimide solution, the modulation mixing solutions is dispersed in carbon black in this mixing solutions.
18. semiconductive polyimide class precursor composition as claimed in claim 17, it is characterized in that, aromatic tetracarboxylic acid's diester more than 2 kinds is by 10～55 moles of % of asymmetry aromatic tetracarboxylic acid diester and 90～45 moles of mixtures that % constituted of symmetry aromatic tetracarboxylic acid diester.
19. semiconductive polyimide class precursor composition as claimed in claim 17, it is characterized in that, aromatic tetracarboxylic acid's diester more than 2 kinds, be by 2,3,3 ' of asymmetry, 10～55 moles of % of 4 '-biphenyltetracarboxyacid acid diester and symmetric 3,3 ', 4,90～45 moles of mixtures that % constituted of 4 '-biphenyltetracarboxyacid acid diester.
20. semiconductive polyimide class precursor composition as claimed in claim 17, it is characterized in that, the high-molecular weight polyimide precursor solution is that number-average molecular weight is the polyamic acid solution more than 10000, and high-molecular weight polyamidoimide solution is that number-average molecular weight is the polyamidoimide solution more than 10000.
21. semiconductive polyimide class precursor composition as claimed in claim 20, it is characterized in that, described number-average molecular weight is the polyamic acid solution more than 10000, reacts manufacturing by biphenyl tetracarboxylic dianhydride and diaminodiphenyl oxide with equimolar amount roughly in organic polar solvent.
22. semiconductive polyimide class precursor composition as claimed in claim 20, it is characterized in that, described number-average molecular weight is the polyamidoimide solution more than 10000, reacts manufacturing by trimellitic acid 1,2-anhydride and the formed acid anhydrides of benzophenone tetracarboxylic dianhydride and aromatic isocyanate with equimolar amount roughly in organic polar solvent.
23. the manufacture method of a semi-conductivity endless tubular polyimide class film is characterized in that, the described semiconductive polyimide class of claim 17 precursor composition is configured as pipe with the spinning-shaping method, carries out heat treated, imidization.
24. the surface resistivity by the described manufacture method manufacturing of claim 23 is 10 7～10 14Ω/, be used for the semi-conductivity endless tubular polyimide class film of the intermediate duplication band of electrofax mode.
25. the manufacture method of a semiconductive polyimide class precursor composition, it is characterized in that, aromatic tetracarboxylic acid's diester more than 2 kinds and aromatic diamine are being dissolved in the nylon salt type monomer solution that forms in the organic polar solvent with equimolar amount roughly, mix high-molecular weight polyimide precursor solution or high-molecular weight polyamidoimide solution, the modulation mixing solutions is dispersed in carbon black in this mixing solutions.
26. the manufacture method of a semi-conductivity high density polyimide precursor composition, it is characterized in that, carbon black is being dispersed in the carbon black dispersion liquid that forms in the organic polar solvent, with dissolving aromatic tetracarboxylic acid's diester of equimolar amount roughly and aromatic diamine.
27. the manufacture method of semi-conductivity high density polyimide precursor composition as claimed in claim 26, it is characterized in that, aromatic tetracarboxylic acid's diester is by 10～55 moles of % of asymmetry aromatic tetracarboxylic acid diester and 90～45 moles of mixtures that % constituted of symmetry aromatic tetracarboxylic acid diester.
28. the manufacture method of semi-conductivity high density polyimide precursor composition as claimed in claim 26, it is characterized in that, aromatic tetracarboxylic acid's diester, be by 2,3,3 ' of asymmetry, 10～55 moles of % of 4 '-biphenyltetracarboxyacid acid diester and symmetric 3,3 ', 4,90～45 moles of mixtures that % constituted of 4 '-biphenyltetracarboxyacid acid diester.
29. the manufacture method of semi-conductivity high density polyimide precursor composition as claimed in claim 26 is characterized in that, measures 100 weight parts with respect to the total of aromatic tetracarboxylic acid's diester and aromatic diamine, carbon black is about 5～35 weight parts.
30. semi-conductivity high density polyimide precursor composition by the described manufacture method manufacturing of claim 26.
31. the manufacture method of a semi-conductivity endless tubular polyimide film is characterized in that, the described semi-conductivity high density of claim 30 polyimide precursor composition is configured as pipe with the spinning-shaping method, carries out heat treated, imidization.
32. the surface resistivity by the described manufacture method manufacturing of claim 31 is 10 7～10 14The semi-conductivity endless tubular polyimide film of the intermediate duplication band of the electrofax mode that is used for of Ω/.
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